Absorbent sheet exhibiting resistance to moisture penetration

ABSTRACT

An absorbent paper sheet is treated with an aqueous wax dispersion such that the sheet includes a fused wax and emulsifier residue in an amount of from about 1 to about 20 weight percent of the sheet based on the combined weight of the fiber, wax residue and an emulsifier residue in the sheet. The fused wax emulsion operates to make at least one surface of the sheet laterally hydrophobic, exhibiting a moisture penetration delay of at least about 2 seconds and less than about 40 seconds as well as a typical contact angle with water at one minute of at least about 50 degrees. There is thus provided absorbent products which exhibit both absorbency and resistance to moisture penetration. The treated sheet further exhibits microbial barrier properties, impeding transfer of bacteria, for example, through the sheet. There are produced tissue products which resist moisture penetration from propelled liquids as well as sequester sorbed liquids in the interior of the tissue.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.11/974,864 of the same title, filed Oct. 16, 2007, now U.S. Pat. No.______. U.S. patent application Ser. No. 11/974,864 was a continuationof U.S. patent application Ser. No. 10/702,414, filed Nov. 6, 2003, nowU.S. Pat. No. 7,300,547. U.S. patent application Ser. No. 10/702,414 wasbased upon U.S. Provisional Application Ser. No. 60/424,434 filed Nov.7, 2002 and also is of like title with this application. The prioritiesof the above applications are hereby claimed and their disclosuresincorporated herein by reference.

TECHNICAL FIELD

The present invention relates generally to absorbent paper sheet such astissue, towel, or the like, treated with a wax dispersion which isheated in situ above the melting temperature of the wax so as to fusethe wax with the web. The absorbent sheet of the invention includes amoisture-penetration resistant layer provided with a laterallyhydrophobic surface.

BACKGROUND ART

Additives or other treatments to enhance the performance of absorbentsheet are well known in the art. There is disclosed in U.S. Pat. No.6,074,525 to Richards a process for increasing bulk of a foreshortenedfibrous web which includes adding moisture to the web at selectedportions, thereby causing the crepe in those portions to relax. Amongthe functional additives which may be present in the added moisture,there are listed softeners, debonders, binders, polyhydroxy compounds,lotions, dispersions, anti-bacterial agents and so forth. See (Col. 10,lines 50-(Col. 11, line 5.

Polymer films have been used on paper products to enhance or providebarrier properties. Barrier performance of polymer films on papersubstrates is a complex process and is influenced by the wicking effectsin the paper. Films may be applied to paper by extrusion or the like orby way of a latex. See FUNDAMENTALS OF BARRIER PROPERTIES, Stannett, V.T. et al., Department of Chemical Engineering, North Carolina StateUniversity, Raleigh, N.C. (undated). Dispersion coating is likewiseknown. For example, there is shown in EP 1103522 A1 a process isdisclosed for application of a polymer coating on a granular activatedcarbon to essentially eliminate or significantly reduce attrition bydusting without a reduction in absorptive velocity or capacity of theactivated carbon. The coatings applied include a high densitypolyethylene dispersion and a silicone dispersion. See EP 1 103522 A1 atpage 5, lines 10 and following.

Composite structures including paper layers are often used in productsrequiring a variety of attributes in the overall performance of theproduct. This is so, in part, because an open paper structure will havegood liquid acquisition properties but poor distribution properties.Multiple layers may accordingly be employed in some absorbent productswhich require a spectrum of properties. One non-woven described in SMARTMATERIALS FOR LIQUID CONTROL, Non-Wovens World, October-November 1999,Dyrmose-Peterson, pages 95-99 includes an upper cover stock layerthermally bonded to a layer combining both desirable liquid acquisitionand distribution properties.

Likewise, composite structures have been used as bed pan liners forexample. See U.S. Pat. No. 3,546,716 to Laumann. The bed pan linerdescribed in the '716 patent includes generally a cold water-solublebase film of synthetic polymeric material, a water insoluble or waterrepellant coating on one side of the base film and tissue paper coveringand adhered to the insoluble coating.

So also, a sheet product including a substrate of non-woven cellulosicfibers, a discontinuous prime coating of hydrophobic material adheringto the cellulosic fibers and a second hydrophilic material filling thesurface voids between hydrophobic material deposits is described in U.S.Pat. No. 3,607,348 to Wray et al. The dual coatings described in the'348 patent render the paper relatively impermeable.

There is described in U.S. Pat. No. 5,399,366 to Geddes et al.multi-layer packaging for hot food. The package includes an absorbentlayer for disposing adjacent the hot food, an extruded barrier filmlayer adjacent the absorbent layer and an outer paper layer adjacent thebarrier layer. The absorbent layer keeps moisture and grease away fromthe hot food (employing a partially hydrophobic or a low-capacitysub-layer) while the barrier layer prevents soak through and retainsheat. Various polymers and waxes are used in the impermeable layer. Seealso U.S. Pat. Nos. 5,560,945; 5,585,129; and 5,609,901 also to Geddeset al.

There has been employed in connection with absorbent paper structures,various means to increase water resistance. There is disclosed in U.S.Pat. No. 1,682,346 to Lorenz a multi-layer paper sheet for wash clothsand the like which will not dissolve during use. At least one layer ismade from pulp which has been sized with resin or latex to impart waterresistance. Indeed, paper structures have been modified or combined withlayers of polymer films in a variety of ways to enhance performance orprovide performance attributes not attainable with paper alone. There isdisclosed in U.S. Pat. No. 3,654,064 to Laumann a multi-layer structureincluding layers of tissue paper and wax for providing a disposablebarrier pro duct. In general, the wax or polymer layer is applied to thepaper substrate by way of extrusion coating. See Col. 4, lines 14 andfollowing. In U.S. Pat. No. 3,612,054 to Matsuda there is disclosed asanitary napkin including a plurality of layers of absorbent materialand at least one barrier sheet of liquid repellant material interposedbetween absorbent layers. The barrier sheet is reported to improvedistribution of liquid within the absorbent material. U.S. Pat. No.4,117,199 to Gotoh et al. discloses a coated paper having a moisture andwater-proof coating thereon produced by coating a paper substrate withan aqueous dispersion containing a synthetic rubber latex and a waxdispersion in various amounts. See Col. 3, lines 25 and following.

U.S. Pat. No. 4,349,610 to Parker discloses a method for improving thewater repellency of a naturally porous, moisture containing paper web bytreating the web with a coating composition containing as its activecoating ingredient an alkyl alkoxysiloxane which reacts with themoisture contained in the paper web to produce a polymer.

U.S. Pat. No. 4,786,367 to Bogart et al. discloses a soft, absorbent andbulky cellulosic fibrous web which has been treated to impart a soothingor emollient effect to the human skin when used for wiping and drying.The agent applied to the web is a lauroamphoglycinate.

U.S. Pat. No. 4,601,938 to Deacon et al., discloses paper towels whichhave been impregnated with a liquid composition. Migration of the liquidalong the length of the paper substrate is substantially prevented bydividing the substrate into a plurality of individual areas by means ofa repeating pattern of liquid-repellant barrier material, for example,wax or certain resins, extending across the width of the substrate.

U.S. Pat. No. 4,789,564 to Kanner et al. discloses that paper may betreated with certain hydridoaminosilanes in order to render thematerials water-repellant.

U.S. Pat. No. 4,816,320 to St. Cyr discloses a multiply tissue for useas cleansing, facial or toilet tissue combining at least one andpreferably two, soft, absorbent layers of loosely felted cellulose fiberpaper and an overlying layer of thin, light-weight moisture resistantcellulose fiber paper with non-skid traction material overlying themoisture resistant layer. The traction material may be a layer ofcellulose fiber paper having a roughened overlying surface or may havean outer coating of finely divided latex particles applied to theoverlying surface of the moisture resistant layer or to a separate,overlying layer. The moisture-resistant layer may be, for example, alayer of glassine paper. See Col. 2, lines 50-55.

U.S. Pat. No. 4,950,545 to Walter et al. discloses facial tissuecontaining a silicone compound exhibiting improved softness and reducedlint while maintaining absorbency. According to the disclosure, thesilicone compound is added in an amount of from about 0.1 to about 5weight percent. See Col. 1, lines 40-45. See, also, U.S. Pat. No.5,227,242 to Walter et al.

In U.S. Pat. No. 4,987,632 to Rowe et al. discloses an absorbent wipingtowel suitable for use in cleaning soiled surfaces in the presence ofwater which includes an absorbent substrate, such as paper, havingapplied thereon a moisture barrier to cover at least 10% of the totalarea of each side of the sheet in such a manner that the moisturebarrier on one side of the sheet coincides with the moisture barrier onthe opposite side so as to form a sandwich. Examples of moisture barriermaterial include wax dispersions applied to the sheet. See Col. 7, lines40 and following.

There is disclosed in U.S. Pat. No. 5,449,551 to Taniguchi a fibrous websuch as tissue paper and non-woven fabrics containing at least one kindof hygroscopic material such as polyhydric alcohols or sugars exhibitinghygroscopicity. According the '551 patent the hygroscopic materialrenders the tissue softer and increases the adhesiveness between fibers,thereby reducing lint.

In U.S. Pat. No. 5,552,187 to Green et al. there is disclosed a fibrousmat-faced gypsum board coated with a water-resistant resinous coating. Apreferred resin for use in connection with these structures is availablein the form of a latex sold by Unicol Chemicals Division of UnicolCorporation under the mark 76 RES 1018. The pH and solids content of thelatex are respectively 7.5-9 and 50%. The resin is a styrene acryliccopolymer which has a relatively low film forming temperature and a Tgof 22° C. See Col. 9, lines 57 and following.

There is disclosed in U.S. Pat. No. 5,601,871 to Krzysik et al. a soft,uncreped through dried tissue product having uniformly distributedsurface deposits of a chemical composition which imparts a reduction inskin irritation during use. Suitable compositions are those which have amelting point of from about 30° C. to about 70° C. and are applied tothe outer surface of the tissue product in melted form, preferably byrotogravure printing. A suitable composition contains an oil, a wax andpreferably a fatty alcohol. Add-on rates may be from about 1% to about40 weight percent of the product. See Col. 3, lines 12 and following.

In some embodiments, the product of the '871 patent is characterized byits hydrophobicity which helps prevent “wet-through” to the users handduring use. This property can be measured in accordance with U.S. Pat.No. 4,950,545 noted above. See also U.S. Pat. No. 5,614,293 and U.S.Pat. No. 5,650,218 to Krzysik et al. as well as: U.S. Pat. No. 5,665,426to Krzysik et al. which discloses a tissue product having uniformlydistributed surface deposits of a solidified composition having amelting point of from about 30° C. to about 70° C.; and U.S. Pat. No.5,885,697 and U.S. Pat. No. 6,187,695 both to Krzysik et al. all ofwhich references disclose tissue products having disposed thereonsurface deposits of a solidified composition having a melting point offrom about 30 to about 70° C. Such compositions include in melted formoils, waxes, and the like. The additive is reported to enhance the feelof the tissue upon the skin.

In U.S. Pat. No. 6,267,842 to Ona et al. there is disclosed awater-based treatment agent for application to tissue paper whichsuppresses a feeling of slipperiness or wetness in ordinary tissue paperso that the paper has a dry touch, ample smoothness and a clean, smooth,tactile impression. The treatment agent includes a silicone oildispersion in which cross-linked silicone particles of a specified sizecontained in the silicone oil droplets are dispersed in water andapplied to the tissue. See Col. 10, lines 5 and following.

There is disclosed in U.S. Pat. No. 5,716,692 to Warner et al. alotioned tissue paper. The lotion composition is applied to the tissuein amounts of from about 5 to about 15 percent by weight. The lotioncomposition includes plastic or fluid emollient such as petrolatum, amixture of petrolatum with alkyl ethoxylate emollient and animmobilizing agent such as a fatty alcohol or a fatty acid to immobilizethe emollient on the surface of the tissue paper web and optionally ahydrophilic surfactant to improve wettability when applied to thetissue.

Various additional methods of influencing liquid migration in a web orcomposite structures are disclosed in the following U.S. Pat. Nos.5,658,639 to Curro et al.; 5,695,487 to Cohen et al.; 5,792,404 to Creeet al.; 5,849,000 to Anjur et al.; 5,932,316 to Cree et al.; 6,015,935to LaVon et al.; 6,025,049 to Ouellette et al.; 6,046,378 to Quincy, IIIet al.; 6,107,539 to Palumbo et al.; 6,180,052 to Ouellette et al.;6,231,948 to Ouellette et al.; 6,232,521 to Bewick-Sonntag et al.;6,383,960 to Everett et al.; 6,403,858 to Quincy, III et al.; and6,416,628 to Huang et al. Curro et al. '639; Cree et al. '404, Cree etal. '316, Oullette et al. '049, '948 and '052, and Bewick-Sonntag et al.'521 relate to increasing the moisture penetration into a web by makinga surface more hydrophobic. Anjur et al. '000 report greaterpermeability when a wettable staple fiber is used with a wettable binderfiber, while La Von et al. enumerates advantages of having enhancedvertical wicking in the crotch area of certain absorbent products andCohen et al. disclose corrugated structures for increasing Z-directionliquid transport. So also, it is seen in U.S. Pat. No. 6,046,378 toQuincy, III, et al. that wettability of synthetic fibers is increased byaltering their surface properties; in this respect, see also Quincy,III, et al. '858, as well as Palumbo et al., '052. The '960 Everett etal. patent discloses composites including superabsorbent polymers andfinally with respect to the patents noted in this paragraph, Huang etal. '628 relates to paperboard impregnated with hydrophobic rosin.

Perhaps more pertinent to the discussion which follows are thereferences noted below.

U.S. Pat. No. 6,332,952 to Hsu et al. discloses a tissue withstrikethrough resistance provided by way of a water-repellant agent suchas sizing agents, waxes, or latexes. Col. 1-2. The sizing agent is addedin an amount of from about 0.5 to 10 pounds per ton of fiber, e.g., fromabout 0.025 to about 0.5 percent by weight, Col. 2, lines 42-46. In someembodiments, the tissue does not contain permanent wet-strength binderresins such as polyamide epichlorohydrin resins. Col. 6, lines 2-11, andthe sizing is sprayed on the tissue after the product is creped from aYankee dryer, or wax, for example, may be added to the furnish before itis applied to the forming fabric by way of a layered headbox. The onlyrepellant agent exemplified is an alkyl ketene dimer. There is disclosedin related PCT publication No. WO 00/00698 (Application No.PCT/US99/14402) a toilet tissue product including a first cellulosic plyand a second cellulosic ply at least one of which has been treated witha repellant agent to prevent fluid from striking through the tissueproduct. The repellent agent is added in an amount of from about 1 toabout 30 pounds per ton of fiber; and more specifically from about 1.2to about 20 pounds per ton of fiber. See Publication No. WO 00/00698 atpage 2, lines 8 and following.

U.S. Pat. No. 6,027,611 to McFarland et al. discloses a process by whichfacial tissue is rendered resistant to water penetration by treating thefibers with a sizing agent prior to forming the sheet, or typicallyafter the sheet is formed. The sizing agent is added in an amount offrom about 1 to about 10 pounds of sizing agent per ton of fiber in thetissue, that is, up to about 0.5 weight percent. See, Col. 2, lines22-26. Typical products have an absorbency rate of from 100-400 second.See, Cols. 2-3.

In U.S. Pat. No. 6,054,020 to Goulet et al. there is disclosed tissueand towel products which resist moisture. Moisture-resistance isimparted by way of amine-modified polysiloxane compounds applied to theouter surfaces of the web. The amount of amine functionality may becontrolled to adjust hydrophobicity to the desired levels which delay,however, allow moisture penetration into the tissue. The siloxane may betypically applied in the form of an dispersion. Add-on rates arespecified to be from about 0.1 to about 5 weight percent. Col. 4, lines12-19. The products of the '020 patent are reported to havecharacteristically long wet-through times and relatively large wet-outareas.

U.S. Pat. No. 5,851,352 to Vinson et al. discloses a multi-ply tissueproduct provided with an internal surface which has deposited thereon astrength agent in an amount of form 0.5 to 10% by weight. The onlystrength resin exemplified is an acrylic latex applied by way of directroto-gravure printing. See Column 25, line 43 and following. Note also anumber of water-soluble materials are enumerated in Col. 7, line 55 andfollowing.

U.S. Pat. No. 6,066,379 to Ma et al. discloses a repulpable,water-resistant paperboard provided with a water-repellant coating whichincludes a polymer matrix, wax and pigment mixture. The paperboard isparticularly well-suited for corrugated products. The water-repellantcoatings are reported to form pinhole-free coatings (Col. 8, line 10 andfollowing) and are applied in amounts of from about 2-3 weight percentof the weight of the paperboard.

U.S. Pat. No. 5,858,173 to Propst, Jr. discloses coating cardboard andthe like with an aqueous acrylic/wax dispersion mixture to providegrease and water resistance. A typical mixture includes 15 parts of ahigh viscosity aqueous acrylic resin dispersion, 65 parts of a lowviscosity aqueous acrylic resin dispersion and 6 parts of an aqueouspolyethylene wax dispersion. The mixture is applied upstream of theheadbox, in the headbox or downstream of the headbox by spraying, forexample. According to the patent, more or less than 3.0-20% by weight ofthe aqueous composition can be incorporated into the stock or finishedpaper. Col. 4, line 4. According to the '173 patent, the describedproduct is repulpable.

SUMMARY OF INVENTION

The present invention relates generally to absorbent paper tissue, toweland the like, wherein the web of cellulosic fibers has been renderedresistant to moisture penetration while generally retaining itsabsorbency. In preferred embodiments the treated webs exhibit physicalproperties such as air permeability and wet tensile strength similar to,or the same as, a like untreated product. A web treated with a fewweight percent wax and emulsifier in accordance with the invention iscapable of exhibiting a contact angle with water almost the same as thewax for a limited time and thus controls the migration of fluid in theweb much more so than one would expect given the relatively small amountof wax present. That is, a small amount of wax can increase the contactangle with water of a cellulosic web, typically 0 degrees, to an initialcontact angle value comparable to wax at about 90 degrees while theabsorbency of the web is maintained. An aqueous wax/emulsifiercomposition applied to the web does not exhibit the desired barrierproperties described herein until the residue is heated above itsmelting point in situ with the web. Without intending to be bound by anytheory, it is believed that the emulsifier operates as a dispersing aidfor the wax and cooperates with the fiber surfaces to disseminate thewax in the web such that the wax has no independent macrostructure andthe wax associates with a great deal of fiber surface area at ahydrophobic surface of the treated web.

A typical process for treating a web in accordance with the inventioninvolves wetting at least one surface of the web with an aqueousdispersion including a wax and an emulsifier and heating the web abovethe melting point of the wax to fuse the wax of the dispersion and toprovide a hydrophobic surface on the web. The hydrophobic surface ismuch more hydrophobic than the web of cellulosic fibers and generallyexhibits a contact angle with water at one minute of 50 degrees or more.

There is thus provided in one aspect of the invention, a method ofmaking an absorbent cellulosic web resistant to moisture penetrationcomprising: (a) wetting at least one surface of the web with an aqueousdispersion including a wax and an emulsifier; and (b) heating the webabove the melting temperature of the wax to fuse the wax of thedispersion and to provide a hydrophobic surface on the web, the waxbeing disposed in the web so that the open interstitial microstructurebetween fibers in the web is substantially preserved and the web has alaterally hydrophobic surface which exhibits a moisture penetrationdelay of at least about 2 seconds as well as a contact angle with waterof at least 50 degrees at one minute of contact time with the web.

The aqueous wax dispersion may be sprayed, printed or otherwise appliedto the web and is optionally dried before heating to a temperature abovethe melting temperature of the wax. Heat may be applied to the web byway of an oven or by way of a Yankee Dryer, an impingement-air dryer, athroughdryer and so forth as is known in the art.

In another aspect, there is provided a method of making a multi-plyabsorbent cellulosic product comprising: (a) wetting at least onesurface of a web with an aqueous dispersion including a wax and anemulsifier; (b) heating the wetted web above the melting temperature ofthe wax to fuse the wax of the dispersion and to provide a hydrophobicsurface on the web, the wax being disposed in the web so that the openinterstitial microstructure between fibers in the web is substantiallypreserved and the web has a laterally hydrophobic surface which exhibitsa moisture penetration delay of at least about 2 seconds as well as acontact angle with water of at least 50 degrees at one minute of contacttime with the web; and (c) plying the web with at least one additionalply.

In a still further aspect, there is provided a method of making a tissueproduct comprising: (a) wetting at least one surface of a web with anaqueous dispersion including a wax and an emulsifier; (b) heating theweb above the melting temperature of the wax to fuse the wax of thedispersion and to provide a hydrophobic surface on the web, wherein thewax is disposed in the web so that the open interstitial microstructurebetween fibers in the web is substantially preserved and the web has alaterally hydrophobic surface which exhibits a moisture penetrationdelay of at least about 2 seconds as well as a contact angle with waterof at least 50 degrees at one minute of contact time with the web; and(c) incorporating the web into a tissue product having a basis weight offrom about 15 to about 30 lbs per 3000 square foot ream, wherein thetissue product exhibits liquid penetration barrier properties such thatless than about 20 percent of liquid sorbed from 0.1 ml of liquidpropelled to one surface of the tissue in a sneeze simulation test willpenetrate to the surface of the tissue product opposite to impact of theliquid.

The foregoing aspects of the invention may be combined independentlywith the Alternative Embodiments enumerated hereinafter which maylikewise be independently combined with one another. The invention alsorelates to a multiplicity of products enumerated hereinafter.

BRIEF DESCRIPTION OF DRAWINGS

The file of this patent contains at least one drawing executed in color.Copies of this patent with color drawings(s) will be provided by thePatent and Trademark Office upon request and payment of the necessaryfee.

The invention is described in detail below with reference to thedrawings, wherein like numerals designate similar parts and wherein:

FIGS. 1A-1F are color photographs and photomicrographs of various pliesof a two-ply napkin of the invention wherein a hydrophobic surface iswetted with blue-dyed water to illustrate barrier properties;

FIGS. 2A-2F are color photographs and photomicrographs of various pliesof a two-ply napkin of the invention wherein a hydrophilic surface iswetted with blue-dyed water to illustrate barrier properties;

FIG. 3 is a schematic diagram of a wax-treated 2-ply towel;

FIG. 4 is an IR chromatogram illustrating wax penetration in the 2 plytowel of FIG. 3;

FIG. 5 is a schematic diagram of a wax-treated air-laid sheet;

FIG. 6 is an IR chromatogram illustrating wax penetration in thewax-treated air laid sheet of FIG. 5;

FIG. 7 is a schematic diagram illustrating a test for measuringresistance to moisture penetration;

FIGS. 8, 9, 10 and 11 are schematic diagrams illustrating testing formoisture penetration of various multilayer arrangements of treatedcellulosic sheet;

FIG. 12 is another schematic diagram for illustrating the microbialbarrier properties of wax-treated cellulosic sheet;

FIG. 13 is a schematic diagram of a paper machine useful for making theabsorbent sheet of the present invention;

FIG. 14 is a schematic diagram illustrating creping angles for producingcreped sheet which may be wax-treated in accordance with the invention;

FIGS. 15A-15D illustrate an undulatory creping blade which may be usedto produce a creped biaxially undulatory sheet shown in FIG. 15E whichmay be wax-treated in accordance with the invention;

FIG. 16 is a schematic diagram of a drying apparatus which may be usedto dry cellulosic sheet and fuse a wax composition applied thereto;

FIG. 17 is a diagram of another drying apparatus which may be used todry cellulosic sheet and fuse a wax composition applied thereto;

FIG. 18 is a schematic diagram of an offset printing and plyingapparatus which may be used to prepare the inventive sheet products;

FIG. 19 is a schematic diagram of a 2-ply, 2-panel folded napkinprepared in accordance with the present invention;

FIG. 20 is a schematic diagram of a 2-ply, 4-panel napkin prepared inaccordance with the present invention;

FIGS. 21A-21J are schematic diagrams illustrating various productionschemes and multi-ply products thereof;

FIGS. 22 and 23 are schematic diagrams illustrating two- and three-plystructures useful for napkins prepared using plies provided with fusedwax treatments in accordance with the invention.

FIG. 24 is a schematic diagram illustrating an absorbent compositewherein the wax-treated absorbent sheet of the invention is used as acover layer for an absorbent core;

FIG. 25A is a view in perspective of a portion of a wax-treated towelwherein the hydrophobic surface thereof is provided with identifyingindicia;

FIG. 25B is a view in perspective of a portion of the opposite side ofthe towel of FIG. 25A wherein the hydrophilic surface thereof has beenprovided with identifying indicia;

FIG. 26A is a schematic diagram illustrating the contact angle of waterwith a sample of treated material;

FIG. 26B is a plot of contact angle versus time for the treated anduntreated side of a basesheet;

FIG. 26C is a plot of contact angle versus time for the treated anduntreated sides of basesheet wherein the melt-fusion time employed wasvaried;

FIG. 26D is a plot of contact angle versus time for the treated anduntreated sides of a basesheet wherein dispersion application pressurewas varied;

FIGS. 27 and 28 are plots of heat flow versus temperature for the firstand second heating respectively of a wax/emulsifier composition;

FIG. 29 is a schematic diagram of a sternutation simulator; and

FIGS. 30-34 are sternutation test results.

DETAILED DESCRIPTION

The invention is described in detail below with reference to the variousexamples and Figures provided herein. Such discussion andexemplification are for purposes of illustration only and is notintended to limit in any way the scope of the present invention.Variations and modifications to various exemplified embodiments withinthe spirit and scope of the present invention, defined in the appendedclaims, will be readily apparent to those of skill in the art.Typically, the treated products of the invention are prepared by wettingan absorbent web with an aqueous wax dispersion including a wax and anemulsifier followed by melt fusing the wax dispersion with the web toprepare a product with at least one hydrophobic surface.

The products of the invention are further appreciated by reference toFIGS. 1A-1F and 2A-2F which are color photographs and photomicrographsin various views of the plies of wax treated napkins which were wettedwith blue-dyed water in order to show barrier and liquid transportproperties. The napkins generally had the two-ply structure shown inFIGS. 19 and 20; that is, one treated ply and one untreated ply. Thenapkins were suspended in a frame as noted in connection with themoisture penetration delay protocol (described hereinafter) in unfoldedform and wetted with blue-dyed water at their upper surface using adropper. The liquid was allowed to spread within the test specimen.After drying the specimens were separated into their constituent pliesand photographed. Representative photographs are appended as FIGS. 1A-1Fand 2A-2F and are further discussed below.

FIG. 1A is a photograph (1×) of the upper surface of a wax treated ply(that is, the upper surface was the surface of the ply to which the waxdispersion was applied) which was wetted with colored water. It can beseen that the point of application in the center of the stain issignificantly darker than the periphery, indicating liquid transportpreferentially in the Z-direction into the sheet. FIG. 1B is aphotograph (1×) of the inner surface of the upper ply, the surface ofthe ply opposite the surface shown in FIG. 1A, again showing the stainmore concentrated at its center. The surface of FIG. 1A typically has acontact angle with water at one minute of about 90° or so, while thesurface of FIG. 1B has a contact angle with water at one minute of about60°-75° or so. In either case, it is seen the hydrophobicity is suchthat moisture preferentially migrates inwardly rather than laterally inthe treated ply.

FIG. 1C is a photograph (1×) of the upper surface of the lower,untreated ply of the test specimen. Here, it is seen the stain isrelatively uniform indicating substantial lateral migration in thehydrophilic ply which typically has a contact angle with water of about0°. Further, FIG. 1D is a photograph (1×) of the opposite surface of thelower hydrophilic ply; that is, the lowermost surface of the testspecimen, which again is relatively uniform indicating substantiallateral migration of moisture. Moreover, it can be seen that FIGS. 1Cand 1D have relatively similar stain intensity indicating relativelyuniform absorption in the untreated ply in all directions.

FIGS. 1E and 1F are color photomicrographs (250×) of the plies of FIGS.1A-1D taken from the side at locations away from the insult but withinthe stain area, respectively. It can be seen in FIG. 1E that the uppersurface of the upper ply is essentially unstained, indicating moisturepenetration substantially in an inward direction and a lack of lateralmoisture migration on the surface. Moreover, it can be seen from FIG. 1Ethat while the lower surface of the upper ply is somewhat stained, thestain extends only about halfway through the ply indicating the fusedwax dispersion acted effectively as a barrier to moisture wicking to thetreated surface from the larger and more concentrated stain in thehydrophilic layer below.

FIG. 1F is a side view of the lower ply of the test specimen in thestain at a location away from the point of insult. Here it is seen thestain is more concentrated and uniform indicating uniform absorption orfluid in all directions and preferential absorption in the lower layer.

In some applications of the invention, it is preferable in many cases toorient the structure so that the point of moisture contact is at ahydrophilic, highly absorbent layer as is seen in FIGS. 2A-2D. In theseFigures, the two ply napkin was oriented so that the treated ply wasoriented downwardly with the surface where wax was applied being thelowermost surface and the uppermost surface where the napkin was wettedin the tests was an untreated ply. Here again, absorbency, moisturemigration and barrier properties are analogous to the features observedwhen the napkin is wetted from the other side.

FIG. 2A is a photograph (1×) of the uppermost surface of the untreatedply which was wetted with the dyed water. It can be seen that the stainis intensive and uniform in the X-Y plane indicating uniform fluidabsorption in all directions.

FIG. 2B is a photograph (1×) of the opposite (internal) surface of theuntreated ply, again showing an intense uniform stain throughout. Thestains in FIGS. 2A and 2B are relatively uniform in all directions andof similar intensity indicating relatively uniform absorption in the X,Y and Z directions in the ply.

FIG. 2C is a photograph (1×) of the upper (inner) surface of the lowertreated ply, while FIG. 2D is a photograph (1×) of the outer surface ofthe treated ply, which has a slightly larger contact angle with waterthan the upper surface of the ply as noted above. Here it is seen thatthe stains of FIGS. 2C and 2D are much less intense than those of FIGS.2A and 2B, indicating resistance to moisture transfer to the ply. Inaddition, the stain at the outer surface (2D) is less intense than atits inner surface (2C) indicating barrier properties within the ply,despite its almost negligible thickness.

FIGS. 2E and 2F are photomicrographs (250×) showing a side view of thestain of FIGS. 2A-2D; FIG. 2E being the upper ply and FIG. 2F being thelower ply. As one might expect from the foregoing discussion, an intenseuniform stain is observed in the upper ply, FIG. 2E. The lower ply (FIG.2F) shows a substantially complete barrier to moisture penetrationwherein the dye terminates before the lower surface of the ply.

As it will be appreciated from the discussion which follows, there arenumerous aspects and variations which may be employed in connection withthe present invention. There is provided in one aspect an absorbentcellulosic web exhibiting resistance to moisture penetration includingan absorbent web of cellulosic fibers provided with a fused waxcomposition in intimate contact with the fibers in the web generallyassimilating the morphology of the fiber surfaces, the fused waxcomposition including a wax and an emulsifier and being disposed in theweb so that the open interstitial microstructure between fibers in theweb is substantially preserved and the web has a laterally hydrophobicsurface which exhibits a moisture penetration delay of at least about 2seconds as well as a contact angle with water of at least 50 degrees atone minute of contact time with the web. The open microstructure isdemonstrated by the air permeation data appearing hereinafter as well asthe appended photomicrographs, typically preserving at least 80 percentof the permeability of an untreated web. The fused nature of the wax isseen in numerous aspects since, for example, the wax does not exhibit anobserved macrostructure of its own either as film or as particles whenviewed at a magnification of 250×. Moreover, the wet strength of the webdoes not change dramatically and the contact angles increase as thewax/emulsion composition is melt-fused in situ with the web for adequatetimes as will be appreciated from the various examples hereinafter.

Typically, the laterally hydrophobic surface of the web exhibits amoisture penetration delay of from about 3 to about 40 seconds withdelay times of 5, 10, or 20 seconds being somewhat typical. The wax isgenerally present in an amount of from about 1 to about 20 weightpercent based on the amount of wax and cellulosic fiber in the web, withfrom about 2 to about 10 weight percent based on the amount of wax andcellulosic fiber in the web being typical. Preferably, there is about 3to about 5 weight percent wax based on the amount of wax and cellulosicfiber in the web.

The wax treatment generally should not prevent the web or sheet fromremaining permeable to air. Generally, the web exhibits an airpermeability of at least 25 percent of the air permeability of a likeweb untreated with the wax and emulsifier composition and typically webexhibits an air permeability of at least 40 percent of the airpermeability of a like web untreated with the wax and emulsifiercomposition. An air permeability of at least 60 percent of the airpermeability of a like web untreated with the wax and emulsifiercomposition is more preferred; while an air permeability of at least 80percent of the air permeability of a like web untreated with the wax andemulsifier composition is even more preferred. In some cases the webexhibits substantially the same air permeability as a like web ofcellulosic fiber untreated with the wax and emulsifier composition.Generally, such air permeabilities are from about 15 to about 45ft³/min-ft² at 0.5 inches of water for paper towel with from about 50 toabout 150 ft³/min-ft² at 0.5 inches of water for lighter basesheet beingsomewhat typical. Air permeabilities of from 5 ft³/min-ft² at 0.5 inchesof water to about 175 ft³/min-ft² at 0.5 inches of water are readilymaintained.

It is likewise preferred not to change the wet strength of the webradically by way of the wax treatment. In general the web exhibits a wettensile strength that is less than about 135 percent of the wet tensilestrength of a like web untreated with the wax and emulsifier compositionand typically the web exhibits a wet tensile strength that is less thanabout 125 percent of the web tensile strength of a like web untreatedwith the wax and emulsifier composition. Still more preferably, the webexhibits a wet tensile strength that is less than about 115 or 110percent of the web tensile strength of a like web untreated with the waxand emulsifier composition and may exhibit substantially the same wettensile strength as a like web of cellulosic fiber untreated with thewax and emulsifier composition. Typically, the web exhibitssubstantially the same dry tensile strength as a like web of cellulosicfiber untreated with the wax and emulsifier composition.

The wax treatment need not have a detrimental effect on absorbency. Ingeneral the treated web exhibits an absorbency of at least 60 percent ofthat of a like web untreated with the wax and emulsifier composition andpreferably the web exhibits an absorbency of at least 75 percent of thatof a like web untreated with the wax and emulsifier composition. Inpreferred cases, the web exhibits an absorbency of at least 90 percentof that of a like web untreated with the wax and emulsifier compositionand still more preferably the web exhibits substantially the sameabsorbency as a like web of cellulosic fiber untreated with the wax andemulsifier composition. Typical absorbencies are at least 2 g/g or 3 g/gand preferably at least 4 g/g. In preferred embodiments, the web has anabsorbency of at least 6-8 g/g.

One way to characterize the inventive products of the invention is bycontact angle with water; hereinafter specified. Cellulosic or paperwebs typically are quite hydrophilic and thus exhibit a contact anglewith water of 0 degrees. The treated webs, on the other hand, typicallyexhibit a contact angle with water of at least about 70 degrees at oneminute of contact time with the web with about 80 degrees at one minuteof contact time with the web being preferred. The treated webs are alsocharacterized as being repulpable, and in some cases dispersible as wellas flushable.

The wax is generally a wax selected from the group consisting ofmicrocrystalline waxes, carnauba waxes, polyolefin waxes such aspolyethylene waxes, polypropylene waxes and polybutene waxes,polyurethane waxes, montan waxes, paraffin waxes, Fischer-Tropsch waxesand mixtures thereof and has a molecular weight in the range of fromabout 500 to about 3000. Melting temperatures of the wax are usuallyless than about 140° C. and more preferably less than 120 degreescentigrade. The melting temperature of the wax is most preferably lessthan about 105° C.; for example, from about 50° to about 105° C. or fromabout 75° to about 105° C.

The applied wax composition usually includes an emulsifier selected fromthe group consisting of anionic emulsifiers, cationic emulsifiers andnon-ionic emulsifiers.

The web of cellulosic fiber may be a creped web of cellulosic fiberhaving, for example a biaxially undulatory structure and may furthercomprise a grease repellant agent, an emollient, a binder and/or across-linking agent. Suitable emollients include emollients or emollientblends known in the art, generally including materials which function tolubricate or moisturize the skin surface, retard moisture, loss, and/ormaintain the skin moisture/vapor balance. Suitable emollients includethose compounds which associate with resolidified lotion to form asmooth, lubricious, nongreasy-feeling layer on the skin. Suitableemollients includes those used in emollient creams and lotions,including liquid hydrocarbons (such as mineral oil, and the like),vegetable and animal fats and oils (such as, lanolin, triglycerides, andthe like), alkyl fatty acid esters (such as methyl, isopropyl, and butylesters of fatty acids, and the like), fatty alcohol esters of benzoicacid, phospholipids (such as lecithin, and the like), and silicones.Emollients are further described in U.S. Pat. No. 5,871,763 to Luu etal. Grease repellants include fluorochemicals, polyvinylalcohol,poly(2-ethyl-2-oxazoline) and the like. Any suitable binder resins maybe used if so desired, water soluble or insoluble depending on theproduct as well as wet strength resins which are well known.Crosslinkers such as zinc inorganic or organic salts may be used withsuitable binders or other resins if so desired.

Unless more specifically defined herein, terms are given their ordinarymeaning and generally accepted test procedures are used. In thediscussion which follows various technical terms are used and testmethods are referred to. Unless otherwise specified or clear from thecontext, ambient conditions are implied, percent means weight percent,predominant and like terminology means more than 50 weight percent.Generally speaking, the present invention relates to absorbentcellulosic sheet as is used in connection with paper towel, paper tissueand related products. This type of paper product is characterized byrelatively high void volume so that it is absorbent as opposed to paperproducts with very low void volumes used in cardboard or paperboardproducts. Absorbent sheet is characterized generally by a void volume ofgreater than about 2 gms/gm, typically from about 4-10 gms/gm. Preferredproducts usually have a void volume of greater than about 5 gms/gm.

The “void volume”, as referred to hereafter, is determined by saturatinga sheet with a nonpolar liquid and measuring the amount of liquidabsorbed. The volume of liquid absorbed is equivalent to the void volumewithin the sheet structure. The void volume is expressed as grams ofliquid absorbed per gram of fiber in the sheet structure. Morespecifically, for each single-ply sheet sample to be tested, select 8sheets and cut out a 1 inch by 1 inch square (1 inch in the machinedirection and 1 inch in the cross-machine direction). For multi-plyproduct samples, each ply is measured as a separate entity. Multiplesamples should be separated into individual single plies and 8 sheetsfrom each ply position used for testing. Weigh and record the dry weightof each test specimen to the nearest 0.0001 gram. Place the specimen ina dish containing POROFIL™ liquid, having a specific gravity of 1.875grams per cubic centimeter, available from Coulter Electronics Ltd.,Northwell Drive, Luton, Beds, England; Part No. 9902458.) After 10seconds, grasp the specimen at the very edge (1-2 millimeters in) of onecorner with tweezers and remove from the liquid. Hold the specimen withthat corner uppermost and allow excess liquid to drip for 30 seconds.Lightly dab (less than ½ second contact) the lower corner of thespecimen on #4 filter paper (Whatman Ltd., Maidstone, England) in orderto remove any excess of the last partial drop. Immediately weigh thespecimen, within 10 seconds recording the weight to the nearest 0.0001gram. The void volume for each specimen, expressed as grams of POROFILliquid per gram of fiber, is calculated as follows:

void volume=[W ₂ −W ₁)/W ₁],

wherein

“W1” is the dry weight of the specimen, in grams; and

“W2” is the wet weight of the specimen, in grams.

The void volume for all eight individual specimens is determined asdescribed above and the average of the eight specimens is the voidvolume for the sample.

The void volume may also be expressed as a “void volume ratio” by usingthe test procedure described above and calculating the percentage weightincrease (PWI) as follows:

The PWI for each specimen, expressed as grams of POROFIL liquid per gramof fiber, is calculated as follows:

PWI=[(W ₂ −W ₁)/W ₁]×100%

wherein

“W₁” is the dry weight of the specimen, in grams; and

“W₂” is the wet weight of the specimen, in grams.

The PWI for all eight individual specimens is determined as describedabove and the average of the eight specimens is the PWI for the sample.

The void volume ratio is calculated by dividing the PWI by 1.9 (densityof fluid) to express the ratio as a percentage. Void volume ratios of300-800 are typical for products of the invention; typically from about400-700.

In order to measure the moisture penetration delay of a surface ofabsorbent sheet, single or multiply, a sample is conditioned at 23° C.and 50% relative humidity. The conditioned sample is secured lightly ina frame without substantial stretching in either the machine orcross-direction, but with sufficient tension in all directions such thatthe sheet is smooth. The sheet is suspended in the frame horizontallysuch that both surfaces of the sheet are not in contact with any othersurface, that is, in contact with air only, since a surface in contactwith the sheet can significantly influence moisture penetration delaytimes. The surface to be characterized is oriented upwardly and a 0.10ml droplet of colored water is placed gently thereon. A timer is startedsimultaneously with the placement of the colored water droplet on thesurface and stopped when the droplet is completely absorbed into thesheet and no longer projects upwardly from the surface as observedvisually with the naked eye. The time is recorded as the moisturepenetration delay. Testing is conducted at room temperature.

The angle defined between a tangent to a liquid droplet surface at itsair/liquid interface at the droplet's line of contact with a solid andthe solid substrate surface upon which the droplet rests (as measuredthrough the liquid) is generally referred to as the contact angle of aliquid with a solid. The contact angle may be measured at any point atthe line of contact of the three phases, air/liquid/solid. “Contactangles” herein refer to contact angles of the absorbent sheet with waterat room temperature as measured with a goniometer. While it was foundthat the sheet of the invention exhibited contact angles which variedsomewhat over time, however, the differences between contact anglesbetween a treated surface and the opposite (untreated) surface thereofremains relatively constant as is seen in Table 9 and FIGS. 26B and 26C.Moreover, since the contact angle of an untreated cellulosic sheet is 0degrees, the absolute increase in contact angle is a reliablequantification of the inventive products. Contact angles reported hereinwere determined by adhering the sample to a 75×25 mm glass microscopeslide. A slide was prepared to receive the sample with a strip ofdouble-sided adhesive tape. A sample ply, typically a basesheet, wasadhered to the tape with the surface to be tested oriented upwardly. Theslide was then placed on the goniometer sample stage and a 0.01 ml dropof distilled water is placed on the surface to be tested. The time isstarted simultaneously with placing the droplet on the sample surfaceand the image of the droplet/sheet sample interface is captured at 1, 3,5, 7, 9 and 11 minutes by the goniometer using a telescopic lensarrangement and video signal recorder. The video signals were analyzedfor contact angle by drawing a tangent vector from the line of contactbetween the water droplet and the sheet surface as illustrated in FIG.26A, discussed in connection with Table 9 below. Any suitable goniometermay be employed. One suitable apparatus is a goniometer available fromRame-Hart Inc., which is operated with Panasonic camera WV-BP312 andused Java based software to measure the contact angle.

Unless otherwise specified, “basis weight” refers to the weight of a3000 square foot ream of product. Likewise, percent or like terminologyrefers to weight percent on a dry basis, that is to say, with no freewater present.

Absorbency of the inventive products is measured with a simpleabsorbency tester. The simple absorbency tester is a particularly usefulapparatus for measuring the hydrophilicity and absorbency properties ofa sample of tissue, napkins, or towel. In this test a sample of tissue,napkins, or towel 2.0 inches in diameter is mounted between a top flatplastic cover and a bottom grooved sample plate. The tissue, napkin, ortowel sample disc is held in place by a ⅛ inch wide circumference flangearea. The sample is not compressed by the holder. De-ionized water at73° F. is introduced to the sample at the center of the bottom sampleplate through a 1 mm. diameter conduit. This water is at a hydrostatichead of minus 5 mm. Flow is initiated by a pulse introduced at the startof the measurement by the instrument mechanism. Water is thus imbibed bythe tissue, napkin, or towel sample from this central entrance pointradially outward by capillary action. When the rate of water imbibationdecreases below 0.005 gm water per 5 seconds, the test is terminated.The amount of water removed from the reservoir and absorbed by thesample is weighed and reported as grams of water per square meter ofsample or grams of water per gram of sheet. In practice, an M/K SystemsInc. Gravimetric Absorbency Testing System is used. This is a commercialsystem obtainable from M/K Systems Inc., 12 Garden Street, Danvers,Mass., 01923. WAC or absorbent capacity (referred to sometimes hereinsimply as “absorbency”) is actually determined by the instrument itself.WAC is defined as the point where the weight versus time graph has a“zero” slope, i.e., the sample has stopped absorbing. The terminationcriteria for a test are expressed in maximum change in water weightabsorbed over a fixed time period. This is basically an estimate of zeroslope on the weight versus time graph. The program uses a change of0.005 g over a 5 second time interval as termination criteria.

Dry tensile strengths (MD and CD), stretch and break modulus aremeasured with a standard Instron test device or other suitableelongation tensile tester which may be configured in various ways,typically using 3 or 1 inch wide strips of tissue or towel, conditionedat 50% relative humidity and 23° C. (73.4), with the tensile lest run ata crosshead speed of 2 in/min. Break modulus is the ratio of peak loadto stretch at peak load.

The wet tensile of the tissue of the present invention is measured usinga three-inch wide strip of tissue that is folded into a loop, clamped ina special fixture termed a Finch Cup, then immersed in a water. TheFinch Cup, which is avail able from High-Tech Manufacturing Services,Inc., Vancouver, Wash. or the Thwing Albert Instrument Company ofPhiladelphia, Pa., is mounted onto a tensile tester equipped with a loadcell with the flange of the Finch Cup clamped by the tester's lower jawand the ends of tissue loop clamped into the upper jaw of the tensiletester. The sample is immersed in water (Standard Water Solution,N9832770, at 23° C. (73° F.), available from Fisher Scientific Company,1600 W. Glenlake Avenue, Itasca, Ill.) and the tensile is tested after a5 second immersion time.

Modulus is measured on a 1″ or 3″ sample using an EJA-1000 TensileTester available from Thwing-Albert Instrument Company, Philadelphia,Pa. and light-weight (50-lb) pneumatic action grips, with rubber coated,1-inch line contact faces, available from Instron Corporation, 100Royall Street, Canton, Mass.

Tensile energy absorption (T.E.A.), which is defined as the area underthe load/elongation (stress/strain) curve, is also measured during theprocedure for measuring tensile strength. Tensile energy absorption isrelated to the perceived strength of the product in use. Products havinga higher T.E.A. may be perceived by users as being stronger than similarproducts that have lower T.E.A. values, even if the actual tensilestrength of the two products are the same. In fact, having a highertensile energy absorption may allow a product to be perceived as beingstronger than one with lower T.E.A., even if the tensile strength of thehigh-T.E.A. product is less than that of the product having the lowertensile energy absorption.

Generally, a paper product is considered repulpable if it is repulpedand reformed into the product wherein the reformed product does notexhibit a substantial increase in wet tensile strength over that of theoriginal product or like product made with untreated fiber. Preferablythere is no increase in either wet tensile or dry tensile. In someembodiments, treated material is dispersible and/or flushable as well. Asheet product is considered dispersible if, when a sample is placed n aflask and shaken at room temperature, disintegrates quickly, typicallyin less than 1000 strokes or so using the following test. Dispersibilityis determined by shaking the sheet gently in water in a 250 ml bottle atroom temperature using a mechanical bottle shaker. The water employed isa standard water solution, Standard Water Solution, NC9832770, at 23° C.(73° F.), available from Fisher Scientific Company. When testing tissue,sheets (or 4.5″×4.5″ specimens) are tested in 3 sheet stacks, awhiledispersible towel is tested in 2 sheet stacks employing 4.5″×4.5″specimens. The bottle shaker is set for a predetermined number ofstrokes and 180 ml of the standard water solution is placed in a 250 mlbottle with an 11/16″ mouth. The specimen stack is carefully rolled upand placed in the bottle with the water. The bottle is immediatelymounted in the bottle shaker which is started and the container isshaken for the predetermined number of strokes. When the shaker stops,dispersibility is checked by inverting the bottle in one quick motionand attempting to pour out the contents. In order to pass the test, theentire contents of the bottle must empty within 8 seconds withoutshaking the bottle. A product is considered flushable if it generallymeets criteria of size and dispersibility.

Calipers reported herein are 8 sheet calipers unless otherwiseindicated. The sheets are stacked and the caliper measurement takenabout the central portion of the stack. Preferably, the test samples areconditioned in an atmosphere of 23°±1.0° C. (73.4°±1.8° F.) at 50%relative humidity for at least about 2 hours and then measured with aThwing-Albert Model 89-II-JR or Progage Electronic Thickness Tester with2-in (50.8-mm) diameter anvils, 539±10 grams dead weight load, and 0.231in/sec descent rate. For finished product testing, each sheet of productto be tested must have the same number of plies as the product is sold.Select and stack eight sheets together. For napkin testing, completelyunfold napkins prior to stacking. For base sheet testing off of winders,each sheet to be tested must have the same number of plies as producedoff the winder. Select and stack eight sheets together. For base sheettesting off of the paper machine reel, single plies must be used. Selectand stack eight sheets together.

On custom embossed or printed product, try to avoid taking measurementsin these areas if at all possible.

Air permeability is measured using a Frazier Air Permeability Tester,available from Frazier Precision Instrument Company, Hagerstown, Md. Airpermeability is defined as the flow rate of air at 23±1° C. through asheet of material under a specified pressure head. It is usuallyexpressed as cubic feet per minute per square foot at 0.50 in. (12.7 mm)water pressure, in cm³ per second per square cm or in units of elapsedtime for a given volume per unit area of sheet. The instrument referredto above is capable of measuring permeability from 0 to approximately5000 cubic feet per minute per square foot of test area.

The term “cellulosic”, “cellulosic sheet” and the like is meant toinclude any product incorporating papermaking fiber having cellulose asa major constituent. “Papermaking fibers” include virgin pulps orrecycle cellulosic fibers or fiber mixes comprising cellulosic fibers.Fibers suitable for making the webs of this invention include: nonwoodfibers, such as cotton fibers or cotton derivatives, abaca, kenaf, sabaigrass, flax, esparto grass, straw, jute hemp, bagasse, milkweed flossfibers, and pineapple leaf fibers; and wood fibers such as thoseobtained from deciduous and coniferous trees, including softwood fibers,such as northern and southern softwood kraft fibers; hardwood fibers,such as eucalyptus, maple, birch, aspen, or the like. Papermaking fiberscan be liberated from their source material by any one of a number ofchemical pulping processes familiar to one experienced in the artincluding sulfate, sulfite, polysulfide, soda pulping, etc. The pulp canbe bleached if desired by chemical means including the use of chlorine,chlorine dioxide, oxygen and so forth. The products of the presentinvention may comprise a blend of conventional fibers (whether derivedfrom virgin pulp or recycle sources) and high coarseness lignin-richtubular fibers, such as bleached chemical thermomechanical pulp (BCTMP).

Absorbent cellulosic webs typically have a heat tolerance limit which,when exceeded by applying too much heat to the web, tends to result inthe degradation of optical properties, i.e., yellowing, and/or thephysical properties of the web. Since many applications of the presentinvention involve products where aesthetics are important, yellowing dueto overheating the web is avoided by employing a wax with a suitablemelting point such that it can be fused on the web without exceeding theheat tolerance limit of the web. One way to characterize the heattolerance limit of a web is the maximum heat input under a given set ofconditions which will not result in a substantial increase in the HunterColor b value of the web. The L, a and b brightness parameters (HunterColor Values) are suitably measured using TA PPI Method T-524-OM-94. Inthe Hunter Color Scheme L, a and b designate color as follows: L denoteslightness increasing form 0 for black to 100 for perfect white, a showsredness when plus, green when minus and zero for grey, b representsyellowness when plus, blueness when minus and zero when grey.Preferably, processing a web without exceeding its heat tolerance limitwill result in a change of no more than about 20% in its Hunter Color bvalue (absolute); and preferably less than that. In practice, the heattolerance limit for a web is a function of the temperature, time attemperature and composition of the web. High lignin fibers such as BCTMPor pulps with significant amounts of secondary fiber will tend to yellowmore and thus will have lower heat tolerance limits when made into websthan webs made from virgin KRAFT fiber, for example. So also, arelatively moist web will be more heat-tolerant. The maximum temperaturewhich can be used depends, in part, upon the time the web is exposed tothe temperature. A drier temperature of 400° F., for example, may besuitable at a processing speed of 500 feet per minute (fpm), but maycause degradation at a line speed of 100 fpm. Thus, one way to avoidexceeding the heat tolerance limit of the web while fusing the wax is toemploy suitable line speeds in a given equipment configuration whileanother way to avoid exceeding the heat tolerance limit of the web is tocontrol the temperature. It will be seen hereinafter that controllingfusing conditions also allows one to control migration of wax into theweb so as to enable particular forms of product with controlled contactangle differences on different surfaces of the web.

Unless otherwise specified, the term “ply” as used herein refers to amonolithic fibrous structure integrally formed on a paper machine, forexample, which may or may not be layered or sided as opposed to multiplyproducts or multiply layers of a product formed by bonding one or moreplies together. The term ply thus includes plies made with amulti-layered headbox with different compositions, whereas the term“layer” and the like includes structures of one or more plies bondedtogether or adjacent one another, as well as layered plies generallyinseparable into constituent plies.

Wax means and includes relatively low melting organic mixtures orcompounds of relatively high molecular weight, solid at room temperatureand generally similar in composition to fats and oils except that theycontain little or no glycerides. Some waxes are hydrocarbons, others areesters of fatty acids and alcohols. Waxes are thermoplastic, but sincethey are not high polymers, are not considered in the family ofplastics. Common properties include smooth texture, low toxicity, andfreedom from objectionable odor and color. Waxes are typicallycombustible and have good dielectric properties. They are soluble inmost organic solvents and insoluble in water. Typical classes of waxesare enumerated briefly below.

Natural waxes include carnauba waxes, paraffin waxes, montan waxes, andmicrocrystalline waxes. Carnauba is a natural vegetable wax derived fromfronds of Brazilian palm trees (Copernica cerifera). Carnauba is arelatively hard, brittle wax whose main attributes are lubricity,anti-blocking and FDA compliance. Carnauba is popular in the can andcoil coating industry as well as the film coating industry. The meltingpoint of carnauba waxes is generally from about 80 to about 86° C.

Paraffins are low molecular weight waxes with melting points rangingfrom about 48° to about 74° C. They are relatively highly refined, havea low oil content and are straight-chain hydrocarbons. Paraffins provideanti-blocking, slip, water resistance and moisture vapor transmissionresistance.

Montan waxes are mineral waxes which, in crude form, are extracted fromlignite formed decomposition of vegetable substances. Typical meltingpoint for montan wax range from about 80 to about 90° C.

Microcrystalline waxes come from the distillation of crude oil.Microcrystalline waxes have a molecular weight of from about 500 to 675grams/mole and melting points of about 73° C. to about 94° C. Thesewaxes are highly branched and have small crystals.

Synthetic waxes include Fischer-Tropsch waxes, polyethylene waxes andwax dispersions of various macromers. Fischer-Tropsch waxes are producedalmost exclusively in South Africa by coal gasification. They includemethylene groups which can have either even or odd numbers of carbons.These waxes have molecular weights of 300-1400 gms/mole and are used invarious applications.

Polyethylene waxes are made from ethylene produced from natural gas orby cracking petroleum naptha. Ethylene is then polymerized to providewaxes with various melting points, hardnesses, and densities.Polyethylene wax molecular weights range from about 500-3000 gms/mole.Oxidized polyethylenes are readily emulsifiable whereas non-oxidizedpolyethylenes largely are not. However, some non-oxidized polyethyleneshave been successfully emulsified. High density polyethylenes (HDPE)have a great deal of crystallinity and their molecules are tightlypacked. Melting points range from about 85° C. to about 141° C. and theyare used in paints, textiles, coatings and polishes. Low densitypolyethylenes display more toughness and exhibit better crystalformation. Densities are from about 0.9 to about 0.95 gms/ml, andmelting points range from 30° C. to 141° C.

Wax dispersions are well known in the art. It is preferred in accordanceto the present invention to employ water-borne wax dispersions as areparticularly well known in the art. In this respect there is noted inU.S. Pat. No. 6,033,736 to Perlman et al.; U.S. Pat. No. 5,431,840 toSoldanski et al., as well as U.S. Pat. No. 4,468,254 to Yokoyama et al.,the disclosure of which patents is incorporated herein by reference. Ingeneral a wax dispersion includes from about 90 to about 50 percentwater, from about 10 to about 50 percent wax solids, and minor amountsof an emulsifier. “Aqueous wax dispersion” and like terminology refersto a stable mixture of wax, emulsifier and water without a substantialsolvent component. The wax is in solid or unmelted form at roomtemperature and the wax dispersion is typically wetted onto the sheetunder ambient or near ambient conditions. The particle size of thedispersion may be greater than or less than 1 micron, with averageparticle sizes of from about 100 nm to about 500 nm being typical foruse in connection with the present invention. Typically, the dispersionsare from 20-50 weight percent solids.

Thermal characteristics of wax dispersions are suitably measuredemploying differential scanning calorimetry (“DSC”). Unless otherwiseindicated, DSC data herein was obtained using the following protocol:(a) hold for 1 minute at −40° C.; (b) heat from −40° C. to 110° C. at10° C. per minute; (c) hold for 1 minute at 110° C.; (d) cool from 110°C. to −40° C. at 10° C. per minute; (e) hold for 2 minutes at −40° C.;(f) heat from −40° C. to 110° C. at 10° C. per minute.

PREFERRED EMBODIMENTS

It has been found in accordance with the invention that wax dispersionssuch as polyethylene wax dispersions, polypropylene wax dispersions,polybutene wax dispersions, polyurethane wax dispersions,polycrystalline was dispersions, carnauba wax dispersions, and carnaubawax blend dispersions, can be used to create a barrier for tissue andtowel products while not impairing their absorbency or adverselyaffecting their look and feel. The treated surface surprisingly has abetter hand feel perception and becomes more hydrophobic than anon-treated sample. Webs may be treated in accordance with the inventionby spraying a wax dispersion containing 20-40 percent solids onto theweb in an amount of from about 3-5 percent or so followed by heating theweb in an oven for 5 minutes at 100° C. when the wax has a meltingtemperature of less than 100° C.

In some embodiments, the fibers under the treated surface appear to bemore hydrophilic than the non-treated sample. Without intending to bebound by any theory, these properties may be due to the micellestructure breaking during contact with the fiber. During this processthe wax may first be disposed on the web surface and the emulsifier(hydrophilic material) component of the dispersion may then migratefurther into the web to improve the fiber wettability. This interactionof a fused wax dispersion with the fiber surface offers a significantadvantage for creating a water barrier without adversely affecting thesoftness and absorbency of the product.

It was also discovered that the water barrier properties of treatedsamples is not affected by the location of the treated surface in theweb structure. The treated surface could be located either outside incontact with the wiping surface or inside of the web structure, as wellas throughout a ply. In the cases where the treated surface is outside,the water barrier functions to reduce the wetted area (i.e., reduce xyor lateral water spreading and promote z direction migration). A lowerwet web surface area is another advantage of the invention as it reducesthe discomfort feeling of a consumer in the case when the product is anapkin (grease barrier) or the product is contacted to the skin for longperiod such as is the case with diapers, and other personal hygieneproducts. Location of the wax in the web is seen in Examples 1 and 2below.

Example 1 Wax Treated 2-Ply Towel

Surface IR chromatography was used to detect wax penetration of aMICHEM® M48040M2 dispersion applied to a 2-ply wet pressed towel usingthe procedure described above. FIG. 3 is a schematic diagram showing anexploded view of the towel 10 having a first ply 12 with a treatedsurface 14 and an inner ply surface 16. Towel 10 is also provided with asecond ply 18 having an inner untreated ply surface 20 and an outeruntreated ply surface 22. These surfaces were compared with an untreatedtowel.

In FIG. 4 there is shown the relevant spectra for the various surfacesof treated 2-ply towel 10, with the wax applied exhibiting a peak at2914 cm⁻¹. The treated surface 14 of ply 12 had a peak height ofapproximately 0.019 absorbance units at this wavelength, while the innerply had a peak height of approximately 0.021 absorbance units indicatingthe wax had fully penetrated the first ply. On the other hand, surfaces20 and 22 of untreated ply 18 exhibited absorbance values of 0.007,roughly equivalent to the surface of an untreated towel indicating thatthe wax had not penetrated to the second ply of the towel.

Example 2 Wax Treated Air-Laid Sheet

Surface IR chromatography was also used to detect wax penetration of aMICHEM® M48040M2 dispersion applied to an air-laid sheet in accordancewith the invention. Here, the (unitary or single ply) sheet was split asshown schematically in FIG. 5. In FIG. 5, there is shown an air-laidsheet 30 having a treated upper surface 32, a middle portion 34 and anuntreated surface 36. The sheet was split along dotted line 38 andspectra were taken at surfaces 32,36 and at the split surface 40proximate to treated surface 32 and the split surface 42 proximate tountreated surface 36. Results appear in FIG. 6. The wax found in themiddle of the sheet was about 50 percent of that on the surface. Thatis, the peak height was 0.116 absorbance units at surface 32 (@ 2915cm⁻¹) but only 0.061 absorbance units (@2915 cm⁻¹) at surface 40. Theabsorbance values found at surfaces 42 and 36 were close to the valuesfor untreated air-laid sheet indicating that the wax did not penetratethe web completely and was retained for the most part on the upper halfof the web.

Examples 3 and 4

These examples demonstrate dramatic changes in water penetration delaywhile permeability and wet tensile remain constant.

2-ply toweling having a basis weight as set forth in Table 1 prepared byconventional wet press technology was sprayed on one side with theamount indicated of a wax dispersion containing approximately 20 to 40percent solids, the solids primarily being waxes having molecular weightin the range of about 500 to 3000 such as paraffins along with naturallyoccurring waxes such as carnauba wax. The approximate melting point ofthe wax mixture was under 100° C. The samples were cured in an oven atapproximately 100° C. for 5 minutes.

The properties of the samples of the invention as compared to thecontrol are set forth in Table 1 which illustrate that the moisturepenetration delay of the treated side increased greatly while airpermeability, dry tensile and wet tensile remained about equal to oronly slightly less than that of the control. The untreated ply did notexhibit an increase in moisture penetration delay.

TABLE 1 Properties of 2-Ply Treated Paper Towel Moisture PenetrationDelay (0.10 ml) Basis GM Dry GM Wet Non Treated Treated Weight TensileTensile Frazier Air Side Side Examples (lb/ream (g/3 in) (g/3 in)Permeability* (Second) (Second) Control (untreated) 31.7 3255 919 31 1 —Example 3 - Treated 33.15 3077 816 31 1 9 4.4 wt % Example 4 - Treated35.48 3213 919 31 1 18.6 10.6 wt. % *ft³/min-ft² at 0.5″ water pressuredrop

As is seen from the above examples which follow, the resistance to waterpenetration of the treated samples increased greatly, even though theair permeabilities are unchanged. As a benchmark, it should be notedthat non-woven polyethylene porous film of the class noted in U.S. Pat.No. 5,658,639 to Curro et al. referenced above has an air permeabilityof 600 ft3/min-ft2 by the foregoing test method.

Examples 5 Through 13 and Comparative Examples A and B

A series of commercially available wax dispersions (available fromMichelman, Inc., Cincinnati, Ohio) were evaluated for their ability toimpart resistance to moisture penetration to paper towel, air-laiddinner napkins and facial tissue. About 5% by weight (dry basis) of anaqueous wax dispersion was applied to a surface of the samples byspraying followed by drying in an oven at 100° C. for 3 minutes. Thesamples were then evaluated for resistance to moisture penetration usingthe procedure illustrated in connection with FIG. 7.

A 1×1 inch square of filter paper 50 was wetted with distilled watercontaining 1% NaCl; about 0.35 g (10 drops) for high basis weightsamples and about 0.175 g (5 drops) for the facial tissue. The wettedfilter paper 50 was placed on a flat surface 52. Two plies of wax heatedsample 54, 56 were placed over the wetted filter paper 50 with theirtreated sides in the interior of the two ply structure at 58, 60 asshown or with the treated surface of the lower ply in contact withwetted filter paper 50.

A 1 lb. weight 62 (also 1×1 inch) was placed over the sample plies 54,56 in alignment with the filter paper to apply 1 psi pressure to thestructure. The weight was left on the high basis weight samples for 10seconds and facial tissue samples for 5 seconds.

In the case of MICHEM® dispersion M48040M2 for paper towel, air-laidnapkins, and facial tissue, no water penetrated the second ply 56 whenthe non-treated ply was placed in contact with the wetted filter paper50.

In the case of air-laid sample, water dispersion in the treated sampleaway from the treated surface was significantly faster than waterdispersion in an untreated ply, indicating that the wax remained on thetreated surface and the emulsifier had migrated into the web to improvethe hydrophilic properties thereof away from the wetted side.

Results for various dispersions are summarized in Table 2 below.

TABLE 2 Moisture Barrier Results and Impact on Sheet Properties SolidsMelting Dispersion Temperature* Results MICHEM ® 48040M2 73-94° C. VeryGood Barrier Microcrystalline wax MICHEM ® Lube 110 85-110° C. GoodBarrier Carnauba Wax MICHEM ® Lube 160 85° C. Good Barrier Carnauba WaxMICHEM ® 44730 105° C. Poor Barrier Polyethylene (A) MICHEM ® 39235 139°C. Poor Barrier Polyethylene (B) MICHEM ® 71646M 91° C. Good Barrier, noimpact Microcrystalline Wax on softness MICHEM ® Lube 124 68-101° C.Good Barrier, untreated Synthetic Wax side also hydrophobic MICHEM ®35160 — Good Barrier, tends to be Polybutylene strong when wetFiberglass X 9 — Coating very stiff Polypropylene MICHEM ® 43040 — GoodBarrier Epolene ® Modified Polypropylene MICHEM ® 59740 — Good Barrier*approximate values reported by manufacturer

As can be seen from the above data, the sheet treated with wax having athreshold melting temperature above 100° C., the temperature to whichthe sample was heated, did not perform well in moisture barrier testing.See Comparative examples A and B. On the other hand, the waxes whichfully melt or are heated above their threshold melting temperatures(e.g., MICHEM® Lube 110) sufficiently to fuse the wax exhibit goodmoisture barrier properties.

The 48040M2 emulsion is an aqueous emulsion typically with about 40%solids including an ethoxylated C18 alcohol (nonionic) emulsifier andmicrocrystalline wax as well as various additives such as poly(ethyleneglycol), dimethyl silicone and triethanolamine. The surfactant may bepresent in an amount of about 0.5-5 percent based on the amount ofsolids (0.75-1.5% in some cases) while the other additives are typicallypresent in the aggregate in an amount of less than 5 percent based onthe weight of solids. Thus, the solids in the emulsion are predominately(more than 50%) wax. The emulsifier may have about 34 ethylene oxiderepeat units, thus being a PEG-1500 nonionic surfactant. The solids aretypically more than 80% by weight wax in suitable microcrystalline waxemulsions.

The 71646M emulsion includes a microcrystalline wax, about 3% of a fattyacid (anionic) surfactant and about 3% triethanolamine, the weight ofthe additives being based on the weight of solids. The surfactant may bea 50:50 blend of stearic and palmitic acid and the emulsion is typicallyabout 45% or so solids.

Examples 14-17

These examples illustrate the synergistic effect of having twocontiguous treated surfaces contacting each other in a multilayerstructure.

Samples of treated toweling were tested for the moisture barrierbehavior generally as noted above by cutting specimen swatches having anapproximate size of five cm by five cm, then placing a pair of thespecimen swatches on a square of filter paper approximately 1 inch on aside wetted with 0.35 grams water in the various configurationsillustrated in FIGS. 8 through 11, that is:

-   -   In Example 14, the lower swatch was placed with its treated side        up while the upper swatch was placed with its treated side down;    -   In Example 15, both of the two superposed specimen swatches were        placed with treated side up;    -   In Example 16, both of the two superposed specimen swatches were        placed with the treated side down;    -   In Example 17, the upper specimen swatch was placed with its        treated side up while the treated side of the lower specimen        swatch was down.

In FIGS. 8, 9, 10 and 11 there are shown two double ply swatches 70,72overlaid on the moistened filter paper 74 which is on surface 76.Swatches 70,72 thus define four layers, two of which have been treatedwith a wax dispersion. In FIGS. 8-11 the treated layers are indicated bythe diagonal lines. The layers are numbered 1, 2, 3 and 4 forconvenience. FIG. 8 shows the multilayer configuration, for Example 14,whereas FIGS. 9, 10 and 11 illustrate the multilayer structures forExamples 15, 16, 17 and 18, respectively.

In each of the arrangements of FIGS. 8-11, an approximately 500 g weight90 was applied to the upper specimen swatch to produce a pressureapproximately one pound per square inch to simulate finger pressure.After 10 seconds the weight was removed and the wetted area of eachsheet was measured. Results are set forth in Table 3.

TABLE 3 Wetted Surface Area (in cm²) of Layers Under 1 PSI PressureTowel Web Example 14 Example 15 Example 16 Example 17 Structure Control(FIG. 8) (FIG. 9) (FIG. 10) (FIG. 11) Top Layer 1 17.2 0 0 8.3 0 PlyLayer 2 17.2 0 14.9 8.3 19.1 Bottom Ply Layer 3 18.5 25 22.7 21.8 20Layer 4 18.5 25 22.7 21.8 20

The multilayer structure exhibited an unexpectedly complete barrier tomoisture penetration when the two treated surfaces of the towel wereplaced in contact with one another (Example 14). In all cases, thetreated sheet exhibited resistance to moisture penetration and increasedwetted areas in some plies over the control, suggesting migration of theemulsifier into the sheet.

Example 18

This Example 18 illustrates the re-pulpable properties of the inventiveproduct. Towel treated with about 10% of fused wax dispersion is pulpedat 2.5% consistency in a blender with water at 38° C. After about 150seconds, the pulp is used to make a hand-sheet. Table 4 illustrates thephysical properties of the hand-sheet re-formed from re-pulped materialprepared in accordance with the invention versus a hand-sheet ofnon-treated towel formed from the same furnish.

TABLE 4 B.W Caliper Dry Tensile Wet Tensile Examples (lb/ream) (mils/1sheet) (G/1 in.) (G/3 in.) Control 40.02 4.286 5327 313 (untreatedsample) Example 18 - 39.77 4.372 3985 207 Treated and Re-pulpedThe results showed that towel product containing wax dispersion isrepulpable because wet tensile of treated hand-sheet does not increase,indeed it is well below the control. Preferably, the dry tensile ofre-formed sheet made form re-pulped material is also no greater than andpreferably lower than the control.

Examples 19, 20

It has also been found that sheets treated with wax dispersions inaccordance with the invention also exhibit microbial barrier properties,as further described in connections with FIG. 12. FIG. 12 is a schematicdiagram illustrating sheets of 2-ply towel or air-laid web which hasbeen provided with a barrier coating of wax dispersion MICHEM® 48040M2and tested for microbial barrier properties as, discussed hereinafter.

Samples of towel and air-laid wipe were submitted for testing toevaluate the ability of a barrier coating treatment to prevent bacteriafrom passing through the sample. The barrier coating treatment has beenapplied to one side of a sheet in accordance with the invention,untreated samples of the same towel and air-laid wipe were provided forthe controls. All the samples were tested as two-layer specimens, thatis, two layers of each sample type were placed on top of each other toform one test specimen. The layers containing the barrier coating offused wax were put together such that the barrier of each layer was inthe center in sandwich form as shown in FIG. 12.

In FIG. 12 there is shown a multilayer structure 100, including 2 sheets102 and 104 of cellulosic sheet to be tested. Treated sheet 102 had anuntreated surface 106 and a treated surface 108 while sheet 104 hadtreated surface 110 and untreated surface 112, such that the treatedsurfaces of the two sheets of the test specimen were in contact witheach other. Untreated sheets were likewise employed for purposes ofcomparison.

The outside surface of 106 was contaminated with bacteria for a tensecond time period. Each of the plies from the contaminated testspecimen was placed on separate Mueller Hinton agar plates. The sampleplys were then removed and the plates incubated. Specifics appear below.

The samples of towel and airlaid wipe were tested with bothstaphylococcus aureus ATCC 25923 and E. coli ATCC 25922. The bacteriawere grown in separate tubes of Mueller Hinton broth. Each broth wasadjusted to a 0.5 MacFarland turbidity standard. A standard serialdilution of this suspension resulting in approximately 10 millionorganisms per mL was then used as the inoculum. The plating media wascommercially prepared, 150 mm, Mueller Hinton agar plates. Each of thesamples were cut into squares which measured 1½ inches by 1½ inches. Twoof the squares were then placed on top of each other such that thetreated sides of the two sheets were in contact and aligned in sandwichstyle with each other as shown. A two layer specimen of either towel orairlaid wipe was placed on a sterile sheet of aluminum foil and theupper surface (A) of sheet 102 inoculated with two drops of bacteria. A2-PSI weight 114 measuring one square inch for a contacting surface wasflame sterilized and then placed on top of the sample for a 10-secondtime period.

For convenience, the sides of the sheets are designated A-D in FIG. 12and in Table 5 and 6.

After inoculation with bacteria, sheet 102 was placed on a MuellerHinton agar plate with the outer surface, Side-A, in contact with theagar. Sheet 104 was then placed on a second agar plated with the bottomside, Side-D, in contact with the agar. A second specimen was preparedin a similar fashion but Side-B, the barrier treated side of sheet 102and Side-C, the barrier treated side of sheet 104 were placed in contactwith the agar.

After a 15 minute time period, the sample sheets were removed and theplates were incubated for 18 hours at 30° C. Visible growth or no growthwas used to indicated effectiveness of the barrier. This procedure wasrepeated for each of the four samples using both staphylococcus aureusand E. coli.

Results are given below in Table 5 for wax-treated paper towel anduntreated paper towel (control).

TABLE 5 Microbial Barrier of Paper Towel Towel Bacterial Growth Treated-Barrier Control MICHEM ®- Bacteria (No Barrier Dispersion Tested PlySide Tested Coating) 48040M2 Staphylococcus 1 A + + aureus B + + 2 C + −D − − E. coli 1 A + + B + + 2 C + − D + −

As will be appreciated from Table 5, the wax-treated towel was superiorto the untreated towel, there being no penetration of the bacteriastaphylococcus aureus or E. coli to the second sheet of the testspecimen.

Results for wax-treated air-laid wipes and untreated wipes (control)appear in Table 6.

TABLE 6 Microbial Barrier of Air-Laid Wipes Airlaid Wipe BacterialGrowth Treated- Barrier Control MICHEM ®- Bacteria (No BarrierDispersion Tested Ply Side Tested Coating) 48040M2 Staphylococcus 1A + + aureus B + + 2 C + − D + − E. coli 1 A + + B + − 2 C + − D − −As can be seen from Table 6 the bacteria was much more effectivelycontrolled in all cases with treatment of the product in accordance withthe invention. In fact, the E. coli was not observed on the bottom ofthe first sheet of air-laid web.

Examples 21 Through 30

These examples illustrate the use of an integratedwet-crepe/after-drying and wax treatment process to produce the sheet ofthe invention.

FIG. 13 illustrates a paper machine wherein a machine chest 170, whichmay be compartmentalized, is used for preparing furnishes that aretreated with chemicals having different functionality depending on thecharacter of the various fibers used. This embodiment shows two headboxes thereby making it possible to produce a stratified product. Theproduct according to the present invention can be made with single ormultiple head boxes and regardless of the number of head boxes may bestratified or unstratified. The treated furnish is transported throughdifferent conduits 160 and 161, where they are delivered to the head box140, 140′ (indicating an optionally compartmented headbox) of a crescentforming machine 130.

FIG. 13 shows a web-forming end or wet end with a liquid permeableforaminous support member 131 which may be of any conventionalconfiguration. Foraminous support member 131 may be constructed of anyof several known materials including photopolymer fabric, felt, fabric,or a synthetic filament woven mesh base with a very fine synthetic fiberbatt attached to the mesh base. The foraminous support member 131 issupported in a conventional manner on rolls, including breast roll 135and couch or pressing roll, 136.

Forming fabric 132 is supported on rolls 138 and 139 which arepositioned relative to the breast roll 135 for pressing the press wire132 to converge on the foraminous support member 131. The foraminoussupport member 131 and the wire 132 move in the same direction and atthe same speed which is in the direction of rotation of the breast roll135. The pressing wire 132 and the foraminous support member 132converge at an upper surface of the forming roll 135 to form awedge-shaped space or nip into which one or more jets of water or foamedliquid fiber dispersion (furnish) provided by single or multipleheadboxes 140, 140′ is pressed between the pressing wire 132 and theforaminous support member 131 to force fluid through the wire 132 into asaveall 142 where it is collected to reuse in the process.

The nascent web W formed in the process is carried by the foraminoussupport member 131 to the pressing roll 136 where the nascent web W istransferred to the drum 146 of a Yankee dryer. Fluid is pressed from theweb W by pressing roll 136 as the web is transferred to the drum 146 ofa dryer where it is partially dried and preferably wet-creped by meansof an undulatory creping blade 147. The wet-creped web is thentransferred to an after-drying section 150 prior to being collected on atake-up roll 148. The drying section 150 may include through-air dryers,impingement dryers, can dryers, another Yankee dryer and the like as iswell known in the art and discussed further below.

Prior to the drying section, there is provided a spray boom 145 whereinan aqueous wax dispersion comprising a wax and an emulsifier is sprayedonto web W in accordance with the invention. The after-drying section150 is operated at a temperature above the melting temperature of thewax so that the dispersion fuses during final drying of the web.

A pit 164 is provided for collecting water squeezed from the furnish bythe press roll 136 and a Uhle box 149. The water collected in pit 164may be collected into a flow line 165 for separate processing to removesurfactant and fibers from the water and to permit recycling of thewater back to the papermaking machine 130.

According to the present invention, an absorbent paper web can be madeby dispersing fibers into aqueous slurry and depositing the aqueousslurry onto the forming wire of a papermaking machine. Any suitableforming scheme might be used. For example, an extensive butnon-exhaustive list includes a crescent former, a C-wrap twin wireformer, an S-wrap twin wire former, a suction breast roll former, aFourdrinier former, or any art-recognized forming configuration. Theforming fabric can be any suitable foraminous member including singlelayer fabrics, double layer fabrics, triple layer fabrics, photopolymerfabrics, and the like. Non-exhaustive background art in the formingfabric area includes U.S. Pat. Nos. 4,157,276; 4,605,585; 4,161,195;3,545,705; 3,549,742; 3,858,623; 4,041,989; 4,071,050; 4,112,982;4,149,571; 4,182,381; 4,184,519; 4,314,589; 4,359,069; 4,376,455;4,379,735; 4,453,573; 4,564,052; 4,592,395; 4,611,639; 4,640,741;4,709,732; 4,759,391; 4,759,976; 4,942,077; 4,967,085; 4,998,568;5,016,678; 5,054,525; 5,066,532; 5,098,519; 5,103,874; 5,114,777;5,167,261; 5,199,261; 5,199,467; 5,211,815; 5,219,004; 5,245,025;5,277,761; 5,328,565; and 5,379,808 all of which are incorporated hereinby reference in their entirety. One forming fabric particularly usefulis Voith Fabrics Forming Fabric 2164 made by Voith Fabrics Corporation,Shreveport, La.

Foam-forming of the aqueous furnish on a forming wire or fabric may beemployed as a means for controlling the permeability or void volume ofthe sheet upon wet-creping. Suitable foam-forming techniques aredisclosed in U.S. Pat. No. 4,543,156 and Canadian Patent No. 2,053,505,the disclosures of which are incorporated herein by reference.

The creping angle and blade geometry may be employed as means toinfluence the sheet properties. Referring to FIG. 14, the creping angleor pocket angle, α, is the angle that the creping rake surface 171 makeswith a tangent 172 to a Yankee dryer at the line of contact of thecreping blade 147 with the rotating cylinder 146 as in FIG. 13. So also,an angle γ is defined as the angle the blade body makes with tangent172, whereas the bevel angle of creping blade 147 is the angle surface171 defines with a perpendicular 174 to the blade body as shown in thediagram. Referring to FIG. 14, the creping angle is readily calculatedfrom the formula:

α=90+blade bevel angle−γ

for a conventional blade. These parameters vary over the creping surfaceof an undulatory blade as discussed herein.

In accordance with the present invention, creping of the paper from aYankee dryer is carried out using an undulatory creping blade, such asthat disclosed in U.S. Pat. No. 5,690,788, the disclosure of which isincorporated by reference. Use of the undulatory crepe blade has beenshown to impart several advantages when used in production of tissueproducts. In general, tissue products creped using an undulatory bladehave higher caliper (thickness), increased CD stretch, and a higher voidvolume than do comparable tissue products produced using conventionalcrepe blades. All of these changes effected by use of the undulatoryblade tend to correlate with improved softness perception of the tissueproducts. These blades, together with high-lignin pulps, cooperate toprovide unexpected and, indeed, dramatic synergistic effect as discussedin connection with the examples below.

FIGS. 15A through 15D illustrate a portion of a preferred undulatorycreping blade 190 useable in the practice of the present invention inwhich a relief surface extends indefinitely in length, typicallyexceeding 100 inches in length and often reaching over 26 feet in lengthto correspond to the width of the Yankee dryer on the larger modernpaper machines. Flexible blades of the patented undulatory blade havingindefinite length can suitably be placed on a spool and used on machinesemploying a continuous creping system. In such cases the blade lengthwould be several times the width of the Yankee dryer. In contrast, theheight of the blade 190 is usually on the order of several inches whilethe thickness of the body is usually on the order of fractions of aninch.

As illustrated in FIGS. 15A through 15D, an undulatory cutting edge 193of the patented undulatory blade is defined by serrulations 196 disposedalong, and formed in, one edge of a surface 192 so as to define anundulatory engagement surface. Cutting edge 193 is preferably configuredand dimensioned so as to be in continuous undulatory engagement withYankee 146 when positioned as shown in FIG. 14, that is, the bladecontinuously contacts the Yankee cylinder in a sinuous line generallyparallel to the axis of the Yankee cylinder. In particularly preferredembodiments, there is a continuous undulatory engagement surface 200having a plurality of substantially colinear rectilinear elongateregions 202 adjacent a plurality of crescent shaped regions 204 about afoot 206 located at the upper portion of the side 208 of the blade whichis disposed adjacent the Yankee. Undulatory surface 200 is thusconfigured to be in continuous surface-to-surface contact over the widthof a Yankee cylinder when in use as shown in FIGS. 13 and 14 in anundulatory or sinuous wave-like pattern.

The number of teeth per inch may be taken as the number of elongateregions 202 per inch and the tooth depth is taken as the height, H, ofthe groove indicated at 201 adjacent surface 208.

Several angles are used in order to describe the geometry of the cuttingedge of the undulatory blade of the patented undulatory blade. To thatend, the following terms are used:

Creping angle “α”—the angle between a rake surface 198 of the blade 190and the plane tangent to the Yankee at the point of intersection betweenthe undulatory cutting edge 193 and the Yankee;

Axial rake angle “β”—the angle between the axis of the Yankee and theundulatory cutting edge 193 which is the curve defined by theintersection of the surface of the Yankee with indented rake surface ofthe blade 190;

Relief angle “γ”—the angle between the relief surface 192 of the blade190 and the plane tangent to the Yankee at the intersection between theYankee and the undulatory cutting edge 193, the relief angle measuredalong the flat portions of the present blade is equal to what iscommonly called “blade angle” or holder angle”, that is “γ” in FIG. 14.

Quite obviously, the value of each of these angles will vary dependingupon the precise location along the cutting edge at which it is to bedetermined. The remarkable results achieved with the undulatory bladesof the patented undulatory blade in the manufacture of the absorbentpaper products are due to those variations in these angles along thecutting edge. Accordingly, in many cases it will be convenient to denotethe location at which each of these angles is determined by a subscriptattached to the basic symbol for that angle. As noted in the '788patent, the subscripts “f”, “c” and “m” refer to angles measured at therectilinear elongate regions, at the crescent shaped regions, and theminima of the cutting edge, respectively. Accordingly, “γ_(f)”, therelief angle measured along the flat portions of the present blade, isequal to what is commonly called “blade angle” or “holder angle”. Ingeneral, it will be appreciated that the pocket angle α_(f) at therectilinear elongate regions is typically higher than the pocket angleα_(c) at the crescent shaped regions.

An undulatory creping blade may be used to produce a creped or recrepedweb as shown in FIG. 15E comprising a biaxially undulatory cellulosicfibrous web 151 creped from a Yankee dryer 146 shown in FIGS. 13 and 14,characterized by a reticulum of intersecting crepe bars 155, andundulations defining ridges 153 on the air side thereof, said crepe bars155 extending transversely in the cross machine direction, said ridges153 extending longitudinally in the machine direction, said web 151having furrows 157 between ridges 153 on the air side as well as crests159 disposed on the Yankee side of the web opposite furrows 157 andsulcations 163 interspersed between crests 159 and opposite to ridges153, wherein the spatial frequency of said transversely extending crepebars 155 is from about 10 to about 150 crepe bars per inch, and thespatial frequency of said longitudinally extending ridges 153 is fromabout 4 to about 50 ridges per inch. It should be understood that strongcalendering of the sheet can significantly reduce the height of ridges153, making them difficult to perceive by the eye, without loss of thebeneficial effects.

The crepe frequency count for a creped base sheet or product may bemeasured with the aid of a microscope. The Leica Stereozoom® 4microscope has been found to be particularly suitable for thisprocedure. The sheet sample is placed on the microscope stage with itsYankee side up and the cross direction of the sheet vertical in thefield of view. Placing the sample over a black background improves thecrepe definition. During the procurement and mounting of the sample,care should be taken that the sample is not stretched. Using a totalmagnification of 18-20, the microscope is then focused on the sheet. Anillumination source is placed on either the right or left side of themicroscope stage, with the position of the source being adjusted so thatthe light from it strikes the sample at an angle of approximately 45degrees. It has been found that Leica or Nicholas Illuminators aresuitable light sources. After the sample has been mounted andilluminated, the crepe bars are counted by placing a scale horizontallyin the field of view and counting the crepe bars that touch the scaleover a one-half centimeter distance. This procedure is repeated at leasttwo times using different areas of the sample. The values obtained inthe counts are then averaged and multiplied by the appropriateconversion factor to obtain the crepe frequency in the desired unitlength.

It should be noted that the thickness of the portion of web 151 betweenlongitudinally extending crests 159 and furrows 157 will on the averagetypically be about 5% greater than the thickness of portions of web 151between ridges 153 and sulcations 163. Suitably, the portions of web 151adjacent longitudinally extending ridges 153 (on the air side) are aboutfrom about 1% to about 7% thinner than the thickness of the portion ofweb 151 adjacent to furrows 157 as defined on the air side of web 151.

The height of ridges 153 correlates with the tooth depth H formed inundulatory creping blade 190. At a tooth depth of about 0.010 inches,the ridge height is usually from about 0.0007 to about 0.003 inches forsheets having a basis weight of 14-19 pounds per ream. At double thedepth, the ridge height increases to 0.005 to 0.008 inches. At toothdepths of about 0.030 inches, the ridge height is about 0.010 to 0.013inches. At higher undulatory depth, the height of ridges 153 may notincrease and could in fact decrease. The height of ridges 153 alsodepends on the basis weight of the sheet and strength of the sheet.

Advantageously, the average thickness of the portion of web 151adjoining crests 159 is significantly greater than the thickness of theportions of web 151 adjoining sulcations 163; thus, the density of theportion of web 151 adjacent crests 159 can be less than the density ofthe portion of web 151 adjacent sulcations 163. The process produces aweb having a specific caliper of from about 2 to about 8 mils per 8sheets per pound of basis weight. The usual basis weight of web 151 isfrom about 7 to about 35 lbs/3000 sq. ft. ream.

Suitably, when web 151 is calendered, the specific caliper of web 151 isfrom about 2.0 to about 6.0 mils per 8 sheets per pound of basis weightand the basis weight of the web is from about 7 to about 35 lbs/3000 sq.ft. ream.

While the products of the invention may be made by way of a dry-crepeprocess, a wet crepe process is preferred in some embodiments,particularly with respect to single-ply towel in some cases. When awet-crepe process is employed, after-drying section 150 may include animpingement-air dryer, a through-air dryer, a Yankee dryer or aplurality of can dryers. The dryer(s) are operated at sufficiently hightemperatures so as to fuse the wax dispersion; however, the papermachines are operated so as not to exceed the heat tolerance limit ofthe web. Impingement-air dryers are disclosed in the following patentsand applications, the disclosure of which is incorporated herein byreference:

-   -   U.S. Pat. No. 5,865,955 of Ilvespaaet et al.    -   U.S. Pat. No. 5,968,590 of Ahonen et al.    -   U.S. Pat. No. 6,001,421 of Ahonen et al.    -   U.S. Pat. No. 6,119,362 of Sundqvist et al.    -   U.S. patent application Ser. No. 09/733,172, entitled Wet Crepe,        Impingement-Air Dry Process for Making Absorbent Sheet, now U.S.        Pat. No. 6,432,267 (Attorney Docket No. 2236); (FJ-99-33).        When an impingement-air after dryer is used, after drying        section 150 of FIG. 13 may have the configuration shown in FIG.        16.

There is shown in FIG. 16 an impingement-air dry apparatus 150 useful inconnection with the present invention. The web is creped off of a Yankeedryer, such as Yankee dryer 146 of FIG. 13 utilizing a creping blade147. The web W traveling in direction S is aerodynamically stabilizedover an open draw utilizing an air foil 220 as generally described inU.S. Pat. No. 5,891,309 to Page et al., the disclosure of which isincorporated herein by reference. Following a transfer roll 222, web Wis disposed on a transfer fabric 224 and subjected to wet shaping by wayof an optional blow box 226 and vacuum shoe 228. The particularconditions and impression fabric selected depend on the product desiredand may include conditions and fabrics described above or thosedescribed or shown in one or more of: U.S. Pat. No. 5,510,002 to Hermanset al.; U.S. Pat. No. 4,529,480 of Trokhan; U.S. Pat. No. 4,102,737 ofMorton and U.S. Pat. No. 3,994,771 to Morgan, Jr. et al., thedisclosures of which are hereby incorporated by reference into thissection.

After wet shaping, web W is transferred over vacuum roll 230impingement-air dry system as shown. The wax emulsion may be sprayed onto the web by way of a spray boom 229 as shown in the diagram. Theapparatus of FIG. 16 generally includes a pair of drilled hollowcylinders 232, 234, a vacuum roll 236 therebetween as well as a hood 238equipped with nozzles and air returns. In connection with FIG. 16, itshould be noted that transfer of a web W over an open draw needs to bestabilized at high speeds. Rather than use an impingement-air dryer,after-dryer section 150 of FIG. 16 may include instead of cylinders 232,234 of a throughdrying unit as is well known in the art and described inU.S. Pat. No. 3,432,936 to Cole et al., the disclosure of which isincorporated herein by reference.

Yet another after-drying section is disclosed in U.S. Pat. No. 5,851,353which may likewise be employed in a wet-creped process.

Still yet another after-drying section 150 is illustrated schematicallyin FIG. 17. After creping from the Yankee cylinder the web W isdeposited on an after-dryer felt 240 which travels in direction 241 andforms an endless lop about a plurality of after-dryer felt rolls such asrolls 242, 244 and a plurality of after-dryer drums such as drums(sometimes referred to as cans) 246, 248 and 250.

A second felt 252 likewise forms an endless loop about a plurality ofafter-dryer drums and rollers as shown. The various drums are arrangedin two rows and the web is dried as it travels over the drums of bothrows and between rows as shown in the diagram. The wax emulsion may besprayed onto the web by way of a sp ray boom 247 as shown. Felt 252carries web W from drum 254 to drum 256, from which web W may be furtherprocessed or wound up on a take-up reel 258.

Examples 21 to 30 illustrate the physical properties of 2-ply embossedtowel products. The towel basesheet is produced at paper machine asshown in FIG. 13 with a throughdryer. MICHEM® 48040M2 was applied by aspray nozzle system positioned after the Yankee dryer and before thethrough air dryer (TAD). The curing temperature in the TAD is about 120°C. The basesheet towel is treated by barrier chemical on the air-side attwo add-on levels 2.6% (low level) and 5% (high level). The towelbasesheet was then converted to the 2-ply towel products with differentcombinations of: (1) non-treated ply with either low or high add-openlevel ply (Examples 22 to 25); (2) two treated plies (Examples 26 to30); and (3) treated side positioned on the inside or the outside of thefinal product (Examples 22 to 30). Physical properties of the productsappear in Table 7 for the 2-ply products.

TABLE 7 Physical Properties Towel Product GM Dry GM Wet Void GM Break GMWeb Structure B.W. Caliper tensile Tensile Volume Modulus ModulusExamples Top Ply Bottom Ply (lb/ream) (mils/8 sht) (g/3 in.) (g/3 in.)Ratio % (g/%) (g/%) Example 21 Non-Treated Non-Treated 29.31 120.0 3568779 630 74.0 303 Example 22 Non-Treated Low-Outside 30.81 125.8 3599 784579 76.7 299 Example 23 Low-Inside Non-Treated 29.80 121.7 3428 679 56477.2 290 Example 24 Non-Treated High-Outside 30.60 125.6 3261 632 63181.1 267 Example 25 High-Inside Non-Treated 30.00 121.8 3369 545 60782.2 281 Example 26 Low-Inside Low-Outside 31.00 126.3 3287 696 547 80.4286 Example 27 Low-Inside Low-Inside 29.80 125.6 2978 714 706 67.8 274Example 28 Low-Outside Low-Outside 30.50 125.8 3301 646 628 85.7 291Example 29 High-Inside High-Inside 38.70 121.8 2491 602 562 69.4 240Example 30 High-Outside High-Outside 31.30 126.3 3179 651 532 82.0 287The samples produced were evaluated for water absorptivity, the resultsbeing somewhat variable with treated samples showing a decrease inabsorptivity as compared to untreated samples. It is thought that thevariability of these results is due to relatively non-uniform spraycharacteristics. More repeatable results are obtained with bettercontrol of spray patterns, overlap and airflow in the spray region. Inany event, these results demonstrate that it is possible to obtainproduct having highly desirable barrier properties on a paper machine byway of spray application of a wax dispersion.

Examples 31-47 2-Ply Napkins

As an alternative to spraying the aqueous wax dispersion onto a basesheet or web W during its manufacture, one may obtain greater uniformityin the coating and accurate loadings by printing the wax onto theabsorbent sheet followed by heating the web in an oven at temperaturessufficient to fuse the wax. Typically, it is desirable to distribute theaqueous dispersion uniformly at the surface (as opposed to distributingthe dispersion in a pattern) by way of offset printing as shownschematically in FIG. 18 with a smooth applicator roll. There is shownin FIG. 18 a printing station 270 provided with a reservoir 272 of asuitable wax dispersion 274. A feed roller 276 is partially immersed inreservoir 272 and rotates in the direction indicated by arrow 278. Feedroller 276 may be provided with a roughened surface or engraved (e.g., agravure roller) to pick up additional fluid as it rotates throughreservoir 272. There is optionally provided a doctor blade 280 to removeexcess dispersion form the roller. Blade 280 may or may not contact feedroller 276, depending on the amount of dispersion desired to betransferred to as an applicator roll 282, and the nature of the surfaceof the feed roll.

Applicator roll 282 has a smooth, resilient surface 284 which contactsfeed roll 276 as shown. Surface 284 receives the dispersion as itrotates in the direction indicated by arrow 286 and prints it onto a webW of absorbent sheet as the sheet travels between applicator roll 282and a backing roll 287 in the direction indicated by arrow 288 whileroll 287 rotates in direction 290. The dispersion is printed ontosurface 291 of web W in any suitable amount; typically in an amount suchthat the web is provided with about 1 to about 20 percent wax based onthe amount of wax and cellulosic fiber in the sheet and then fused in anoven indicated at 292. The emulsifier is likewise present in the sheet,but typically in much smaller amounts since the emulsifier is generallypresent in amounts of less than 5 percent of the total solids in thedispersion.

There is optionally provided a conduit 305 for providing heated airindicated by arrow 307 to the surface of applicator roll 282 and onexhaust conduit 311 acting as a return in a flow direction indicated byarrow 309. The dispersion to be printed on the sheet is raised in solidsat this point by using heated air to remove excess water. This watercannot be removed prior in the process because viscosities become toohigh. However at this point, as long as the material can be transferredto the web, water can be removed irrespective of the viscosity rise. Insome cases, a “skin” may form over the material from the rapid dryingand the base material may even “melt” or begin to melt which will permiteven higher water removal while “sealing” the web so that the remainingwater and desired material do not migrate into the sheet. Therefore lessmaterial need be applied to achieve desired effects. Likewise, heat canbe provided to applicator roll 282 by any suitable means includingelectric coils, hot oil, steam and so forth in order to achieve thedesired results.

Web W may be plied with another web W′ at a calendar or embossingstation 294 as web W advances along the direction indicated generally byarrow 296. Web W and web W′ are bonded together in a nip 298 by lightpressure between a pair of rolls 300, 302 which rotate in directions 304and 306, respectively, to make a 2-ply napkin product, for example, asshown at 308. There is preferably provided an adhesive or glue betweenthe plies to promote bonding between fibers of the plies. Alternatively,basesheet may be plied and then wax-treated.

2-ply sheet 308 is converted into 4-panel and 2-panel napkins having thefold/treated side arrangements illustrated schematically in FIGS. 19 and20.

Referring to FIG. 19, there is shown a 2-panel napkin 310 made from a2-ply sheet 312 including a first untreated ply 314 bonded to a secondwax-treated ply 316. There is provided a single fold 318 between a firstpanel 320 and a second panel 322. Napkin 310 is thus configured to havetwo outer untreated surfaces, such as surface 324 and two internaltreated hydrophobic surfaces 326, 328 which are provided with a fusedwax treatment. Surfaces 326, 328 are contiguous when the napkin isfolded flat providing a highly effective moisture barrier.

In FIG. 20 there is shown a 4-panel napkin 330 having folds at 332 andat 334. Napkin 330 has two plies 346, 348 bonded to each other. Ply 346is made from untreated base sheet while ply 348 is prepared with 4-5percent of a fused wax composition in accordance with the invention. Thevarious panels accordingly have the following properties: surface 350 isuntreated base sheet and is relatively hydrophilic; surface 352 iswax-treated and is laterally hydrophobic; surface 354 is alsowax-treated and laterally hydrophobic; surfaces 356, 358 are untreatedbase sheet and are relatively hydrophilic; surfaces 360 and 362 arewax-treated and laterally hydrophobic; and surface 364 is untreated andrelatively hydrophilic.

Napkin 330 thus has two interfaces made up of two contiguous hydrophobicsurfaces. It has been found that the 4-fold napkin is substantiallyimpenetrable to moisture when folded flat. Even teaspoon-size liquidinsults do not penetrate the napkin. In testing, consumers observingthis phenomenon indicated a strong preference for the product, includinga purchase interest of over 90%. A purchase interest of 75% or more isunusual, while values above this such as 90% or more are remarkable.

In Table 8 there is provided properties of 2-panel and 4-panel 2-plynapkins wherein one ply has been provided with a fused wax treatmentafter the basesheets had been plied. Four different basesheets wereplied and the first ten thousand (10,000) feet of each roll waswax-treated by offset printing and fused at 350° F. at 150 feet perminute. The next ten thousand (10,000) feet were run as a control. Therolls were converted into 2-panel and 4-panel napkins and evaluated. Itis seen in Table 8, the wax treatment does not substantially effectphysical properties or absorbency; yet moisture penetration is greatlyreduced as noted above.

TABLE 8 2 and 4-Panel Napkin Properties T.E.A. T.E.A. Caliper BasisTensile MD CD mils/ Weight Tensile CD Stretch Stretch mm- mm- 8 shtlb/3000 ft{circumflex over ( )}2 MD g/3 in g/3 in MD % CD %gm/mm{circumflex over ( )}2 gm/mm{circumflex over ( )}2 4-Panel NapkinsTreated 50.08 18.74 1304 343 10.3 5.3 0.993 0.142 Untreated 53.50 18.691316 396 15.5 6.2 1.312 0.184 Treated 66.00 22.10 856 312 11.2 7.0 0.6780.170 Untreated 74.28 21.93 795 342 13.3 6.9 0.701 0.166 Treated 83.3826.23 702 245 9.6 6.9 0.449 0.127 Untreated 93.28 26.41 741 280 14.7 7.50.683 0.153 Treated 55.38 20.28 1583 610 7.2 5.6 0.855 0.273 Untreated66.58 20.21 1558 683 10.0 6.7 1.040 0.325 Grand 67.81 21.82 1,106.74401.31 11.46 6.50 0.84 0.19 Avg Untreated 71.91 21.81 1,102.24 425.2113.35 6.81 0.93 0.21 Avg Treated 63.71 21.84 1,111.23 377.41 9.57 6.200.74 0.18 Avg 2-Panel Napkins Treated 59.30 18.75 1167 334 9.13 7.10.788 0.183 Untreated 67.23 18.82 1318 346 13.4 7.7 1.173 0.192 Treated77.5 22.31 854 361 11.4 6.7 0.681 0.181 Untreated 83.45 22.44 919 41016.2 8.5 0.983 0.258 Treated 91.65 26.68 730 273 11.1 7.2 0.544 0.149Untreated 103.33 26.69 629 277 12.5 9.2 0.471 0.191 Treated 63.85 20.601537 570 6.4 5.3 0.696 0.237 Treated 66.18 20.54 1499 646 7.4 5.5 0.7970.275 Untreated 77.60 20.41 1557 668 10.3 6.9 1.093 0.337 Grand 76.9021.92 1,134.33 431.77 10.89 7.13 0.80 0.22 Avg Untreated 82.90 22.091,105.70 425.42 13.09 8.09 0.93 0.24 Avg Treated 72.11 21.78 1,157.22436.85 9.13 6.37 0.70 0.20 Avg Wet Wet Tens Tens Finch Finch Cured-Cured- MD Modulus Modulus Modulus Absorb. CD g/ GM CD MD Capacity g/3 in3 in g/% Stretch g/% Stretch g/% Stretch g/g 4-Panel Napkins Treated 91182 28.8 20.7 40.2 8.59 Untreated 81 236 21.2 21.3 21.1 8.72 Treated 3568 19.0 16.7 21.7 8.92 Untreated 28 64 13.5 12.9 14.1 9.28 Treated 18 5314.2 12.1 16.6 9.05 Untreated 23 37 11.5 11.3 11.6 9.69 Treated 149 36144.2 37.0 53.1 8.25 Untreated 124 269 31.7 31.9 31.4 8.71 Grand 68.61158.69 23.02 20.49 26.24 — Avg Untreated 63.89 151.51 19.46 19.38 19.56— Avg Treated 73.33 165.87 26.57 21.61 32.02 — Avg 2-Panel NapkinsTreated 76 249 23.9 16.9 33.8 9.07 Untreated 69 239 17.2 14.2 20.7 10.0Treated 34 59 20.5 19.8 21.2 9.09 Untreated 29 66 15.9 16.3 15.5 9.41Treated 19 56 14.5 12.9 16.4 9.78 Untreated 23 48 11.2 10.6 11.9 10.23Treated 145 342 41.0 34.8 48.3 8.35 Treated 155 340 40.5 36.5 45.1 8.31Untreated 126 264 30.0 27.8 32.4 9.48 Grand 74.96 184.98 23.85 21.0927.26 — Avg Untreated 61.60 154.47 18.57 17.25 20.12 — Avg Treated 85.64209.39 28.08 24.16 32.96 — Avg

As will be appreciated from the foregoing discussion and data, theprocess of preparing a base sheet to exhibit the desired barriercharacteristics involves applying aqueous barrier chemicals to the sheetand then removing the water followed by curing the barrier material. Itis seen above that the barrier chemicals do not completely seal thesheet since air permeability changes only slightly with propertreatment. That is, the natural porosity and surface texture of thesheet is retained to a great degree. This indicates most of the barrierchemical is located on the top surfaces of the fibers that make up thesheet and that very little of it “bridges” the spaces between fibers.Therefore, the barrier properties in use arise from the non-wettablesurface properties of these exposed fibers. Further experiments haveshown that with pressure, water can be forced through the open areas,again confirming that the porosity of the sheet remains intact. We havefound that unless great care is taken, some of the water based barrierchemistry penetrates into the sheet structure and through to the otherside of a treated sheet. While this backside of the sheet usuallydoesn't provide as much moisture barrier as the treated side, the degreeto which this penetration is allowed affects the initial contact angleof wetting fluids and also may reduce the overall water holding capacityof these sheets. Still further work has shown that the surfacecharacteristics of both sides of a treated ply of tissue, napkin, andtowel paper affect the subsequent converting of cured sheets intomultiply products.

Typically, plies are attached to make a finished product like a towel ornapkin by embossing with or without adhesive to affect a physicalattachment by the close proximity of two closely spaced elements of theembossing press. With conventional products, ply attachment generallyincreases with increased loadings in the embossing press. However, whenusing cured barrier treated plies of the invention, increased embosspressing loading without adhesive does not suffice to bond a treated plyto an untreated ply. Even when the embossing process introduced tearsinto the sheet from excessive loading no effective ply attachment wasobserved. So also, adhesive should be applied to a treated surface aswill be appreciated from the discussion which follows.

Attempts to apply adhesive to untreated ply and then combine that withtreated and cured ply failed to generate sufficient ply attachment, evenat high levels of glue application. It was then discovered that if thegluing material is first applied to the treated ply sufficient plyattachment is generated even at low, cost-effective, addition rates.Without intending to be bound by any theory, we believe that when theglue is applied to the untreated ply some of the material moves into thesheet structure while leaving sufficient glue on the surface to attachanother ply of similar wetting properties. But when the residual gluecomes into contact with the treated ply, the pressure applied forces therest of the glue into the untreated ply rather than affecting adhesionto the treated ply. We believe this is due to the inability of theprocess to “push” the adhesive material beyond the surface treatedfibers in the z-direction into the structure so that contact withuntreated (or lesser treated) fibers beneath the surface. Based uponthis experience, it was quite surprising that we could, in fact, printthe adhesive onto the treated ply. We believe that when the adhesive isapplied to the treated ply, the pressure in the printing nip causes thematerial to move past the treated surface fibers into the structure ofthe sheet, thus locking the material to the surface. The adhesivematerial that remains on the surface is then sufficient to adhere theuntreated ply as in a normal operation. In the various multi-plymanufacturing schemes illustrated below, adhesive is preferably appliedin accordance with the foregoing discussion, particularly when thebarrier coating is cured prior to plying with an untreated ply. Anysuitable adhesive may be employed, for example, poly(vinyl alcoholbased) adhesives, cellulose ether based adhesives, hot melt adhesives,or any known to the skilled artisan.

Various preferred production schemes and products are summarized brieflyin FIGS. 21A through 21J.

In FIG. 21A there is shown web, W, being provided to a printing station370 wherein a wax emulsion is printed onto the underside 372 of web W.WebW, is thereafter plied with web W′ and the emulsion is melt-fused toproduce the two-ply product 374 of FIG. 21B. Product 374 includes afirst ply 376 with a treated inner surface 378 as well as an untreatedply 380. Similarly, the inventive products may be produced using a pairof applicator rolls as shown in FIG. 21C where webs, W and W′ are pliedat a pair of applicator rolls 382, 384 as the webs move in the directionindicated to form the product 389 of FIG. 21D which has two plies 386,388 with wax-treated outer surfaces 390, 392.

Another two-ply product 394 may be prepared using a wax/emulsifierapplication apparatus as is shown in FIG. 21E. Here, the wax dispersionis applied to webs W and W′ as they travel in the direction indicated ontheir inner surfaces 396,398 by applicator rolls 400,402 as shown. Thewebs are thereafter plied at embossing station 404 and the emulsion isfused with the web to form product 394 shown in FIG. 21F wherein theproduct has two internal treated surfaces 396, 398 to prevent moisturepenetration.

Three-ply products may be produced by way of the application schemesshown in FIGS. 21G and 21. In FIG. 21G, wax dispersion is printed onboth sides of web W as it travels through station 370 by applicatorrolls 406, 408 before the web W is plied with webs W′ and W″ atembossing station 410. The product has the structure shown in FIG. 21H,with two outer plies 412, 414 as well as an inner ply 416 which has beentreated on surface 420 adjacent ply 412 as well as on surface 422adjacent ply 412. Alternatively, web W, web W′ and web W′″ may be pliedwhile rolls 406, 408 provide the aqueous wax dispersion to the outsideof the three-ply structure as is shown in FIG. 21I. The three-plyproduct, shown in FIG. 21J includes outer plies 424, 426 with outerwax-treated surfaces 428, 430 as well as an internal untreated ply 432.

Particularly preferred layer structures for napkins are shownschematically in FIGS. 22 and 23. In FIG. 22 there is shown thecross-section of a 2-ply napkin 431 having plies 433 and 435. Ply 433has an inner layer 437 which is provided a fused wax treatment so thatit has a laterally hydrophobic region at 437 and ply 435 is provided afused wax treatment at 439 so that this region is hydrophobic as well.The two contiguous hydrophobic regions in the plied structure exhibitthe synergistic barrier properties noted above; whereas, outer regions441, 443 of the napkin are relatively hydrophilic.

Another preferred napkin structure is shown schematically in FIG. 23. A3-ply napkin 445 is provided with untreated outer plies 447, 449 and aninner ply 451 which has been provided on one or both sides a fused waxtreatment in accordance with the invention.

The inventive absorbent sheet of the invention is advantageouslyemployed in connection with facial tissue, bath tissue, paper toweling,napkins, shop towels and the like and is also useful as a cover layerfor an absorbent composite since the treated surface resists lateralmigration of moisture, minimizing discomfort, for example, associatedwith a wetted incontinence garment such as diaper. There is shownschematically in FIG. 24 a cross-section of a composite useful for suchapplications.

The composite is provided with a cover sheet 472 made from wax-treatedcellulosic sheet prepared in accordance with the invention. Cover sheet472 has a wax-treated outer surface 474 which is laterally hydrophobicas noted above such that applied moisture at surface 474 migratesinwardly in the direction of arrow 476 at the surface and tends tomigrate laterally (i.e., in the direction of the plane of the sheet)below surface 474, as shown by arrows 478.

An absorbent cellulosic core 480 may be made from non-woven cellulosicsheet, such as air-laid sheet and is optionally impregnated withsuperabsorbent polymer particles indicated at 482. The superabsorbentpolymer is typically a polymer of acrylic acid as is well known in theart. Sheet 472 is preferably adhered to core 480.

Inasmuch as moisture penetrates surface 474 in a direction perpendicularto the plane of sheet 472, the wetted area at surface 474 is minimized.

A shop towel 490 may be prepared from an air-laid web treated inaccordance with the invention on one side 492 to be laterallyhydrophobic on that side and create a barrier to migration from itsother relatively hydrophilic side 494. In such cases, shownschematically in FIGS. 25A and 25B, it may be convenient to mark thetowel appropriate indicia, for example, a “D” on the hydrophobic sideand a “W” on the hydrophilic side as shown so that a user will readilyascertain the appropriate orientation of the towel if he or she wishesto keep their hands dry, for example, when using the towel. Instead ofletters as identifying indicia, designs, colors and so forth may beemployed for this purpose.

Examples 48A Through 52B

The following examples illustrate the effect of the inventive fused waxtreatment on the contact angle of the surface of a treated sheet. A highcontact angle can be achieved by a “light” treatment of a denseconstruction or a “high” treatment of an open structure. A large contactangle difference describes the conditions for z-direction wicking whichis responsible for pulling the water from the treated surface andleaving it “dry” to the touch. In diaper or incontinence productconstruction, a “high” contact angle outer surface (e.g. polypropylene)is used on the skin-side and the urine/menses is “pushed” into theabsorbent outer layer by overlying hydrostatic pressure or pressure ofcontact against the skin. The required pressure to push the liquid intothe absorbent layer can be calculated from the LaPlace equation: Δp=2 gcos θ/r; where g is the liquid surface tension, θ is the liquid contactangle and r is the pore radius. Δp values >0 signify a wetting conditionand is the internally applied pressure necessary to prohibit liquidintrusion. Also the rate of wicking into the absorbent structure isgoverned by the Washburn equation: V=rg cos θ/(4μh); where r is the poreradius, g=liquid surface tension and θ is the liquid/solid contactangle, μ is liquid viscosity and h is height of liquid penetration inthe web.

To demonstrate the effect of the fused wax dispersion on thehydrophobicity of the sheet, basesheet was prepared as described abovetreated on one side with 6.2% by weight (dry basis) with MICHEM® waxdispersion 48040M2. The contact angle over time for five samples on thetreated side (side A) and the untreated side (side B) were measuredusing the procedure noted hereinabove. The contact angle is thus definedat the line of contact between the air (A), liquid droplet (L) andbasesheet (S) as is seen in FIG. 26A, where the contact angle (θ) isshown between the surface (S) and the tangent vector X_(A) at the airside of the droplet. While values of θ varied somewhat over time, thedifferences between contact angles of opposite sides of the sheetremained relatively constant. Results appear in Table 9, and averagecontact angles over time for the samples appear graphically in FIG. 26B.

TABLE 9 Contact Angle Sample No. Time Applied Side (A) Back Side (B)(min) 48A 49A 50A 51A 52A Avg SD Wgt 48B 49B 50B 51B 1 93 99 90 98 9294.4 3.912 6.54 82 74 75 72 3 84 94 80 87 85 86.0 5.148 3.77 72 71 68 705 82 90 76 81 84 82.6 5.079 3.88 65 68 68 70 7 80 89 73 78 81 80.2 5.8052.97 65 64 68 68 9 78 88 69 75 80 78.0 6.964 2.06 62 62 67 67 11  77 8767 73 77 76.2 7.294 1.88 59 60 67 62 Sample No. Time Back Side (B)Difference (min) 52B Avg SD Wgt 1 2 3 4 5 Avg SD Wgt 1 80 76.6 4.2195.26 11 25 15 26 12 17.8 7.190 1.93 3 76 71.4 2.966 11.36 12 23 12 17 914.6 5.505 3.30 5 73 68.3 2.950 11.49 17 22 8 11 11 13.8 5.630 3.15 7 7067.0 4.449 16.67 15 25 5 10 11 13.2 7.497 1.78 9 67 65.0 2.739 13.33 1626 2 8 13 13.0 9.000 1.23 11  67 63.0 3.808 6.90 18 27 0 11 10 13.210.035 0.99 14.267 Avg Difference  6.560 Std Dev  2.934 SE (Avg)  2.776t (4, 0.975)  6.121 95% Two-Sided LCL for Avg 22.412 95% Two-Sided UCLfor Avg  2.132 t (4, 0.95)  8.012 95% One-Sided LCL for Avg

Based on the data of Table 9, the average difference between contactangles, treated side and untreated sides, was about 14 degrees, with a95% confidence level that the average difference in contact anglebetween the two sides was from about 6 to about 22. The treated side hada contact angle of at least 8 degrees more than the untreated side witha confidence level of 95%.

The contact angle measured by the method noted herein of untreatedbasesheet after 1 or 2 seconds is very small (approximately 0°) and thusit appears that the wax penetrated the sheet from one surface to theother in the tests conducted, but remained more concentrated on thetreated side for the sheet tested in Table 9. It has been found that theeffect of the wax can be tailored by controlling the time, temperatureand pressure involved in disseminating the wax into the sheet asdiscussed further below.

Examples 53 Through 57

Utilizing generally the application technique described in connectionwith FIG. 18, the oven temperature was adjusted to 350° F. (177° C.) andthe machine speed varied while preparing basesheet provided with a fusedwax dispersion. The oven had a length of about 12 feet such that thedryer residence time was from about 0.8 seconds to about 4.8 secondsbased on machine speeds of 150 and 900 feet per minute, respectively.Contact angles were measured on the treated (applied) side and theuntreated side of the sheet. Results appear in FIG. 26C wherein it canbe seen at high machine speeds (low residence times) the effect oncontact angles of the basesheet was markedly lower.

In another series of runs, the application nip gap between an applicatorroll (i.e., roll 282 of FIG. 18) and its backing roll 287 was variedbetween low gap (high pressure), normal gap and large gap (low pressure)while applying the dispersion to the sheet. The gap was generally variedbetween 0.002-0.010 inches, about 60% of the dry sheet caliper or less.Contact angles were measured and appear in FIG. 26D. In FIG. 26D it isseen that the high gap/low pressure application of the dispersionincreased the “sidedness” of the ply.

Examples 58-65

The wax treatment of the invention was applied to a variety ofcommercial base sheets which were then compared with untreated basesheet for air permeability and dispersibility. That is to say, theproperties of a treated web are compared with a like untreated web inTable 10.

TABLE 10 Comparison of Air Permeability/Dispersibility Frazier Air Perm.(*) Dispersibility (*) Example # Product (Ft{circumflex over( )}3/min/ft{circumflex over ( )}2) (Strokes to Pass) 58 CommercialBasesheeet 117 ± 4 26 Non-Treated 59 Commercial Basesheet 118 ± 6 30Treated 60 Commercial Basesheet  155 ± 15 44 Treated 61 CommercialBasesheet 166 ± 9 64 Treated 62 Commercial Basesheet 104 ± 4 1500 (1)(Napkin) Non-Treated 63 Commercial Basesheet 114 ± 5 1500 (2) (Napkin)Treated 64 Facial Tissue 157 ± 6 1500 (1) Non-Treated 65 Facial TissueTreated 151 ± 2 1500 (2) (*) Sample size is 4.5 in. × 4.5 in. - (1 ply)(1) Samples passed the test but wetted sheets were still intact (2)Samples failed to pass the test at 1500 strokes

It can be seen in Table 10 that the wax treatment did not substantiallychange the permeability of any of the webs, which exhibited more or lessthe same Frazier Air Permeabilities as untreated product. Examples 58and 59 exhibited similar dispersibilities, while in other cases thedispersibility of the products appeared to decrease slightly aftertreatment with wax.

The dispersions including the wax and emulsifier show relatively complexmelt behavior as will be appreciated from Table 11 below which is asummary of the DSC data obtained on the 48040M2 material. As can beseen, multiple heat absorbing peaks are absorbed; FIG. 27 is a firstheating plot of heat flow versus temperature for the solids of theemulsion. FIG. 28 is a plot of heat flow versus temperature for thesecond DSC heating of the sample of FIG. 27 wherein it can be seen thatone or more of the prominent enthalpy peaks shift to a lower temperatureindicative of the fused wax treatments of the invention. It is believedthe emulsifier interacts with the wax in the melt to lower one or moreof the composition's characteristic melting temperatures of anywherefrom 1 to 20 degrees centigrade or so. That is to say, the waxcomposition fused with the fibers of the web (after melting) differsfrom that applied to the web (before melting) as seen from the differentmelt characteristics observed on the first and second heating of thesolids of the dispersion.

TABLE 11 Thermal Characteristics of Michem ® Emulsion 48040M2 TotalPEAKS Euthalpy Peak #1 Peak #2 Peak #3 Δ11 T_(peak) ΔH T_(peak) ΔHT_(peak) ΔH Sample (J/g) (° C.) % (J/g) (° C.) % (J/g) (° C.) % (J/g)Dry First 165.2 30.0 7.7 12.7 42.4 11.0 18.3 59.4 53.3 88.1 MichemEmulsion Heating Second 157.4 — — — 35.1 15.8 24.9 51.2 53.6 84.4Heating Liquid First — — — — — — 60 — — Michem Emulsion Heating Second —— — — — — — — — Heating PEAKS Peak #4 Peak #5 Peak #6 T_(peak) ΔHT_(peak) ΔH T_(peak) ΔH Sample (° C.) % (J/g) (° C.) % (J/g) (° C.) %(J/g) Dry First 90.3 18.0 29.7 98.0 10.0 16.4 — — — Michem EmulsionHeating Second 87.1 20.8 32.8 98.3 7.9 12.4 103.0 1.9 2.9 Heating LiquidFirst 90 — — — — — 101*  — — Michem Emulsion Heating Second — — — — — —— — — Heating

Tissue Products

The resistance to moisture penetration provided by way of the inventionis particularly effective in tissue products where the combination ofresistance to penetration and limited migration of liquids on a treatedsurface cooperate to enable the production of tissues with outersurfaces which retain relatively low amounts of liquid even when theproduct is insulted with pressure-propelled liquid as occurs with asneeze, for example. This feature becomes apparent by way of simulatedsternutation or sneeze testing, described further below.

There is shown schematically in FIG. 29 an apparatus 500 including acompressed air source 510 provided with a timer and an air brush 512coupled to source 510 and communicating with a liquid supply 514. Airbrush 512 also communicates with a chamber 516 as shown. Chamber 516encloses one side of a tissue sample 520 while a second chamber 522encloses the other side of sample 520, which is secured on sample plate524. The tissue sample employed has a multiplicity of plies, such asplies 526, 528 and 530. The sample chambers (in combination) areavailable from VWR Scientific Products (Cat. #282000-301), and anysuitable air brush, such as a Vega 600 air brush may be used. Samplesare prepared with individually separable plies so that liquid sorptionand sequestering characteristics can be identified.

Apparatus 500 is operated as follows:

-   -   Set the compressed air regulator with timer to 20 psig and a 0.5        second dispense time;    -   Adjust the needle of the airbrush so the amount of liquid is        about 0.105±0.005 g. The blue color water contains 1% of NaC+1%        293C BLUE;    -   Record the weight of each single ply tissue (m_(n)) of the test        sample before testing (n is the ply number of the sample);    -   Place the sample in between the chamber 522 and the Sample Plate        (1.5 inch diameter hole) and close the chambers 516 and 522 with        a clip;    -   The sample side facing the airbrush (chamber 516) is referred to        as the Nose-Side, and the opposite side, chamber 522 is referred        to as the Hand-Side. This side of the tissue sample is tested to        see how much water penetrates through the sheet;    -   Press the start button on the compressed air regulator. This        will supply 0.105±0.005 g of liquid in 0.5 second and also        create about 1 psig pressure inside the chamber 516;    -   Remove the clip and open the chambers to remove the wetted        sample; and    -   Record the weight of each wetted ply tissue (M_(n)).

Following testing, the water distribution (percent) of each ply, n, ofthe sample is calculated by the following formula:

Water Distribution of Ply n (%)=(M _(n) −m _(n))×100/Σ(M _(n) −m _(n))

Examples 66-107

Following the above procedures, samples prepared from plies of tissuesheet enumerated in Table 12 were tested in the configuration indicatedin Table 13. N indicates an untreated ply, whereas T indicates a plytreated in accordance with the invention. The sample structure indicatedis from the Nose-Side (ply #1) to the Hand-Side in the tables and inFIGS. 30-34. Tissues A through I indicate commercially availableproducts. Most of the commercial products are sold as two or three plyproducts, and tissue I is sold as a lotioned product. The treated tissuebasesheet of the invention (T) had a basis weight of 9.37 lbs/3000square foot ream.

Sternutation test results appear in Table 13 and in FIGS. 30-34 forselected test samples.

TABLE 12 Single Ply Basis Weight Samples (lb/ream) Treated Basesheet (T)9.37 Tissue A 10.64 Tissue B 9.30 Tissue C 8.57 Tissue D 8.67 Tissue E8.67 Tissue F 10.86 Tissue G 9.05 Tissue H 12.22 Tissue I 14.70

TABLE 13 Water Distribution (%) Total Sample Ply 1 Ply 6 Amount Ref.(#) - Ply Structure Nose-Side Ply 2 Ply 3 Ply 4 Ply 5 Hand-Side (g)Tissue A 3 - Ply NNN 35 35 30 — — — 0.107 4 - Ply NNNN 25 23 27 25 — —0.105 6 - Ply NNNNNN 16 18 15 18 18 15 0.100 Tissue A 3 - Ply NTN 61 2712 — — — 0.102 Basesheet (N) 3 - Ply TNT 35 51 14 — — — 0.107 With 4 -Ply NTTN 67 32 1 0 — — 0.104 Treated 4 - Ply TNNT 25 37 37 1 — — 0.104Basesheet (T) 4 - Ply TNTN 39 55 6 0 — — 0.106 4 - Ply NTNT 36 22 37 5 —— 0.094 5 - Ply NNTNN 47 48 5 0 0 — 0.100 6 - Ply NNTTNN 48 42 10 0 0 00.100 6 - Ply NTNNTN 30 10 29 30 1 0 0.097 6 - Ply TNTTNT 34 54 12 0 0 00.101 Tissue B 3 - Ply NNN 34 35 31 — — — 0.108 4 - Ply NNNN 29 29 23 19— — 0.105 6 - Ply NNNNNN 25 19 16 14 14 12 0.094 Tissue B 3 - Ply NTN 5822 20 — — — 0.110 Basesheet (N) 4 - Ply NTTN 78 20 2 0 — — 0.105 With4 - Ply TNNT 20 40 38 2 — — 0.101 Treated 6 - Ply NNTTNN 45 48 7 0 0 00.113 Basesheet (T) 6 - Ply NTNNTN 30 10 29 30 1 0 0.097 Tissue C 3 -Ply NNN 36 35 29 — — — 0.112 (2 - Ply) 4 - Ply NNNN 24 23 27 25 — —0.111 6 - Ply NNNNNN 17 16 16 16 18 17 0.100 Tissue D 3 - Ply NNN 33 3433 — — — 0.102 (2 - Ply) 4 - Ply NNNN 29 27 25 19 — — 0.105 6 - PlyNNNNNN 27 18 17 14 15 9 0.101 Tissue E 3 - Ply NNN 46 40 14 — — — 0.121(3 - Ply) 4 - Ply NNNN 42 31 16 11 _(—) _(—) 0.113 6 - Ply NNNNNN 42 3518 5 0 0 0.106 Tissue F 3 - Ply NNN 39 33 28 — — — 0.107 (2 - Ply) 4 -Ply NNNN 42 34 19 5 — — 0.107 6 - Ply NNNNNN 42 32 17 6 3 0 0.116 TissueG 3 - Ply NNN 45 38 17 — — — 0.114 (2 - Ply) 4 - Ply NNNN 34 21 27 18 —— 0.104 6 - Ply NNNNNN 35 29 17 9 7 3 0.100 Tissue H 3 - Ply NNN 55 2916 — — — 0.106 Extra Strength 4 - Ply NNNN 55 36 7 2 — — 0.105 6 - PlyNNNNNN 51 32 15 2 0 0 0.094 Tissue I 3 - Ply NNN 60 27 13 — — — 0.114(Lotion) 4 - Ply NNNN 59 27 14 0 — — 0.114 6 - Ply NNNNNN 54 28 18 0 0 00.107

The results show that regardless of basis weight, the treated tissueproducts performed better or at least comparably to all of the productstested in terms of Hand-Side dryness. Given that moisture does notlaterally migrate on an outer ply, the tissues of the invention thusprovide a tissue product where both outer surfaces are relatively low inmoisture content after insulted with propelled liquid, a highlydesirable feature since tissue with these attributes will minimizepenetration through the tissue as well as reduce “red nose” irritationresulting from contact with a wet tissue surface.

Quite remarkably, it is seen in FIGS. 30-32 that in the samples testedwith internal untreated plies and outer treated plies, that liquid ispreferentially sequestered between the outer surfaces of the tissuesample, notwithstanding the relatively high velocity of the insult. Withconventional products, one ordinarily sees a relatively evendistribution of liquid or a continuously decreasing concentration(nose-to-hand) as is seen for conventional products of relatively highbasis weight in FIGS. 33 and 34.

The invention has been described in detail with reference to variousembodiments; however, modifications to those embodiments within thespirit and scope of the invention will be readily apparent to those ofskill in the art. The invention is defined in the appended claims andfurther described in the following Alternative Embodiments of theinvention.

Alternative Embodiments

There is provided in a first alternative embodiment (AlternativeEmbodiment No. 1) an absorbent cellulosic web exhibiting resistance tomoisture penetration comprising an absorbent web of cellulosic fibersprovided with a fused wax composition in intimate contact with thefibers in the web, the fused wax composition including a wax and anemulsifier fused in situ with the web and being disposed in the web sothat the open interstitial microstructure between fibers in the web issubstantially preserved and the web has a laterally hydrophobic surfacewhich exhibits a moisture penetration delay of at least about 2 secondsas well as a contact angle with water of at least 50 degrees at oneminute of contact time with the web.

Alternative Embodiment No. 2 is the absorbent web exhibiting resistanceto moisture penetration according to the first alternative embodiment,wherein the laterally hydrophobic surface of the web exhibits a moisturepenetration delay of from about 3 to about 40 seconds.

Alternative Embodiment No. 3 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 2,wherein the laterally hydrophobic surface of the web exhibits a moisturepenetration delay of at least about 5 seconds.

Alternative Embodiment No. 4 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 3,wherein the laterally hydrophobic surface of the web exhibits a moisturepenetration delay of at least about 10 seconds.

Alternative Embodiment No. 5 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 4,wherein the laterally hydrophobic surface of the web exhibits a moisturepenetration delay of at least about 20 seconds.

Alternative Embodiment No. 6. is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein wax is present in an amount of from about 1 to about 20 weightpercent based on the amount of wax and cellulosic fiber in the web.

Alternative Embodiment No. 7 is the absorbent sheet exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 6, wherein wax is present in an amount of from about 2 to about 10weight percent based on the amount of wax and cellulosic fiber in theweb.

Alternative Embodiment No. 8 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 7,wherein wax is present in an amount of from about 3 to about 5 weightpercent based on the amount of wax and cellulosic fiber in the web.

Alternative Embodiment No. 9 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web exhibits an air permeability of at least 25 percent ofthe air permeability of a like web untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 10 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 9,wherein the web exhibits an air permeability of at least 40 percent ofthe air permeability of a like web untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 11 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 10,wherein the web exhibits an air permeability of at least 60 percent ofthe air permeability of a like web untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 12 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 11,wherein the web exhibits an air permeability of at least 80 percent ofthe air permeability of a like web untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 13 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 12,wherein the web exhibits substantially the same air permeability as alike web of cellulosic fiber untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 14 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web exhibits an air permeability of from about 15ft³/min-ft² to about 45 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 15 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 14,wherein the web exhibits an air permeability of from 50 ft³/min-ft² toabout 150 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 16 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web exhibits a wet tensile strength that is less than about135 percent of the wet tensile strength of a like web untreated with thewax and emulsifier composition.

Alternative Embodiment No. 17 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 16,wherein the web exhibits a wet tensile strength that is less than about125 percent of the wet tensile strength of a like web untreated with thewax and emulsifier composition.

Alternative Embodiment No. 18 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 17,wherein the web exhibits a wet tensile strength that is less than about115 percent of the wet tensile strength of a like web untreated with thewax and emulsifier composition.

Alternative Embodiment No. 19 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 18wherein the web exhibits a wet tensile strength that is less than about110 percent of the wet tensile strength of a like web untreated with thewax and emulsifier composition.

Alternative Embodiment No. 20 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 19,wherein the web exhibits substantially the same wet tensile strength asa like web of cellulosic fiber untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 21 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web exhibits substantially the same dry tensile strength asa like web of cellulosic fiber untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 22 is the absorbent cellulosic web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 1, wherein the web exhibits an absorbency of at least 60 percent ofthat of a like web untreated with the wax and emulsifier composition.

Alternative Embodiment No. 23 is the absorbent cellulosic web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 22, wherein the web exhibits an absorbency of at least 75 percent ofthat of a like web untreated with the wax and emulsifier composition.

Alternative Embodiment No. 24 is the absorbent cellulosic web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo 23, wherein the web exhibits an absorbency of at least 90 percent ofthat of a like web untreated with the wax and emulsifier composition.

Alternative Embodiment No. 25 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 24,wherein the web exhibits substantially the same absorbency as a like webof cellulosic fiber untreated with the wax and emulsifier composition.

Alternative Embodiment No. 26 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web exhibits an absorbency of at least 3 g/g.

Alternative Embodiment No. 27 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 26,wherein the web exhibits an absorbency of at least 6 g/g.

Alternative Embodiment No. 28 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 27,wherein the web exhibits an absorbency of at least 8 g/g.

Alternative Embodiment No. 29 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the hydrophobic surface of the web exhibits contact angle withwater of at least about 70 degrees at one minute of contact time withthe web.

Alternative Embodiment No. 30 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the hydrophobic surface of the web exhibits contact angle withwater of at least about 85 degrees at one minute of contact time withthe web.

Alternative Embodiment No. 31 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web is repulpable.

Alternative Embodiment No. 32 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web is dispersible.

Alternative Embodiment No. 33 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the web is flushable.

Alternative Embodiment No. 34 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the wax comprises a wax selected from the group consisting ofmicrocrystalline waxes, carnauba waxes, polyolefin waxes such aspolyethylene waxes, polypropylene waxes and polybutene waxes,polyurethane waxes, montan waxes, paraffin waxes, Fascher-Tropsch waxesand mixtures thereof.

Alternative Embodiment No. 35 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 34,wherein the wax is a microcrystalline wax.

Alternative Embodiment No. 36 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 35,wherein the wax dispersion includes an emulsifier selected from thegroup consisting of anionic emulsifiers and non-ionic emulsifiers.

Alternative Embodiment No. 37 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 36,wherein the wax is a carnauba wax.

Alternative Embodiment No. 38 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 37,wherein the dispersion comprises a non-ionic emulsifier.

Alternative Embodiment No. 39 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the wax has a molecular weight in the range of from about 500 toabout 3000.

Alternative Embodiment No. 40 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the melting temperature of the wax is less than about 140° C.

Alternative Embodiment No. 41 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 40,wherein the melting temperature of the wax is less than about 120° C.

Alternative Embodiment No. 42 is the absorbent sheet exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 41, wherein the melting temperature of the wax is less than about105° C.

Alternative Embodiment No. 43 is the absorbent sheet exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 42, wherein the melting temperature of the wax is from about 50° toabout 105° C.

Alternative Embodiment No. 44 is the absorbent sheet exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 43, wherein the melting temperature of the wax is from about 75° toabout 105° C.

Alternative Embodiment No. 45 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,wherein the cellulosic web is a creped cellulosic web.

Alternative Embodiment No. 46 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 45,wherein the cellulosic web has a biaxially undulatory structure.

Alternative Embodiment No. 47 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,further comprising a grease repellant agent.

Alternative Embodiment No. 48 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,further comprising an emollient.

Alternative Embodiment No. 49 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,further comprising a binder.

Alternative Embodiment No. 50 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 1,further comprising a cross-linking agent.

Alternative Embodiment No. 51 is an absorbent cellulosic web exhibitingresistance to moisture penetration comprising an absorbent web ofcellulosic fibers provided with a fused wax composition in intimatecontact with the fibers in the web generally assimilating the morphologyof the fiber surfaces, the fused wax composition including a wax and anemulsifier and being disposed in the web so that the open interstitialmicrostructure between fibers in the web is substantially preserved andwherein the web exhibits an absorbency of at least 3 g/g.

Alternative Embodiment No. 52 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 51,wherein the web exhibits an absorbency of at least 6 g/g.

Alternative Embodiment No. 53 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 52,wherein the web exhibits an absorbency of at least 8 g/g.

Alternative Embodiment No. 54 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 51,wherein the web exhibits an air permeability of from about 15ft³/min-ft² to about 45 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 55 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 51,wherein the web exhibits an air permeability of from about 50ft³/min-ft² to about 150 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 56 is a sided absorbent cellulosic webexhibiting resistance to moisture penetration having a first and secondsurface comprising an absorbent web of cellulosic fibers provided with afused wax composition in intimate contact with the fibers in the webgenerally assimilating the morphology of the fiber surfaces, the fusedwax composition including a wax and an emulsifier and being disposed inthe web so that the open interstitial microstructure between fibers inthe web is substantially preserved and such that the fused wax isconcentrated at the first surface of the web and decreases inconcentration in a direction toward the second surface whereby the webhas a laterally hydrophobic surface exhibiting a moisture penetrationdelay of at least about 3 seconds.

Alternative Embodiment No. 57 is the sided absorbent web according toAlternative Embodiment No. 56, wherein the web has a laterallyhydrophilic surface exhibiting a moisture penetration delay of less than2 seconds.

Alternative Embodiment No. 58 is the sided absorbent sheet exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 57, wherein the wax treated laterally hydrophobic first surfaceexhibits a moisture penetration delay of from about 3 to about 40seconds.

Alternative Embodiment No. 59 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 58, wherein the laterally hydrophobic first surface exhibits amoisture penetration delay of at least about 5 seconds.

Alternative Embodiment No. 60 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 59, wherein the laterally hydrophobic first surface exhibits amoisture penetration delay of at least about 10 seconds.

Alternative Embodiment No. 61 is the sided absorbent sheet exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 60, wherein the laterally hydrophobic first surface exhibits amoisture penetration delay of at least about 20 seconds.

Alternative Embodiment No. 62 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 56, wherein the web exhibits an air permeability of at least 40percent of the air permeability of a like web untreated with the wax andemulsifier composition.

Alternative Embodiment No. 63 is the sided absorbent exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 62, wherein the web exhibits an air permeability of at least 60percent of the air permeability of a like web untreated with the wax andemulsifier composition.

Alternative Embodiment No. 64 is the sided absorbent exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 63, wherein the web exhibits an air permeability of at least 80percent of the air permeability of a like web untreated with the wax andemulsifier composition.

Alternative Embodiment No. 65 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 64, wherein the web exhibits substantially the same air permeabilityas a like web of cellulosic fiber untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 66 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 56, wherein the web exhibits an air permeability of from about 15ft³/min-ft² to about 45 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 67 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 56, wherein the web exhibits an air permeability of from about 50ft³/min-ft² to about 150 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 68 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 56, wherein the web exhibits a wet tensile strength that is lessthan about 135 percent of the wet tensile strength of a like webuntreated with the wax and emulsifier composition.

Alternative Embodiment No. 69 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 68, wherein the web exhibits a wet tensile strength that is lessthan about 125 percent of the wet tensile strength of a like webuntreated with the wax and emulsifier composition.

Alternative Embodiment No. 70 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 69, wherein the web exhibits a wet tensile strength that is lessthan about 115 percent of the wet tensile strength of a like webuntreated with the wax and emulsifier composition.

Alternative Embodiment No. 71 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 70, wherein the web exhibits a wet tensile strength that is lessthan about 110 percent of the wet tensile strength of a like webuntreated with the wax and emulsifier composition.

Alternative Embodiment No. 72 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 71, wherein the web exhibits substantially the same wet tensilestrength as a like web of cellulosic fiber untreated with the wax andemulsifier composition.

Alternative Embodiment No. 73 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 56, wherein the web exhibits substantially the same dry tensilestrength as a like web of cellulosic fiber untreated with the wax andemulsifier composition.

Alternative Embodiment No. 74 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 56, wherein the web exhibits an absorbency of at least 60percent of that of a like web untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 75 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 74, wherein the web exhibits an absorbency of at least 75percent of that of a like web untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 76 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 75, wherein the web exhibits an absorbency of at least 90percent of that of a like web untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 77 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 76, wherein the web exhibits substantially the same absorbency as alike web of cellulosic fiber untreated with the wax and emulsifiercomposition.

Alternative Embodiment No. 78 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 56, wherein the web exhibits an absorbency of at least 3 g/g.

Alternative Embodiment No. 79 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 78, wherein the web exhibits an absorbency of at least 6 g/g.

Alternative Embodiment No. 80 is the sided absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 79, wherein the web exhibits an absorbency of at least 8 g/g.

Alternative Embodiment No. 81 is the absorbent web exhibiting resistanceto moisture penetration according to Alternative Embodiment No. 56,wherein the hydrophobic surface of the web exhibits contact angle withwater of at least about 50 degrees at one minute of contact time withthe web.

Alternative Embodiment No. 82 is an absorbent cellulosic web exhibitingresistance to moisture penetration comprising an absorbent web ofcellulosic fiber and the fused residue of an aqueous wax dispersionapplied to one side thereof, wherein the sheet has a laterallyhydrophobic surface and a relatively hydrophilic surface such that thecontact angle of the laterally hydrophobic surface with water is atleast about 5 degrees greater than the contact angle of the relativelyhydrophilic surface with water.

Alternative Embodiment No. 83 is the absorbent cellulosic web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 82, wherein the contact angle of the laterally hydrophobic surfacewith water is at least about 10 degrees greater than the contact angleof the relatively hydrophilic surface with water.

Alternative Embodiment No. 84 is the absorbent cellulosic web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 83, wherein the contact angle of the laterally hydrophobic surfacewith water is at least about 20 degrees greater than the contact angleof the relatively hydrophilic surface with water.

Alternative Embodiment No. 85 is the absorbent cellulosic web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 84, wherein the contact angle of the laterally hydrophobic surfacewith water is at least about 40 degrees greater than the contact angleof the relatively hydrophilic surface with water.

Alternative Embodiment No. 86 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 85, wherein the contact angle of the laterallyhydrophobic surface with water is at least about 80 degrees greater thanthe contact angle of the relatively hydrophilic surface with water.

Alternative Embodiment No. 87 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, incorporated into a multi-ply absorbent product.

Alternative Embodiment No. 88 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, having a single-ply monolithic web structure.

Alternative Embodiment No. 89 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, wherein the hydrophobic surface exhibits a moisturepenetration delay of from about 3 to about 40 seconds.

Alternative Embodiment No. 90 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 89, wherein the hydrophilic surface exhibits a moisturepenetration delay of less than 2 seconds.

Alternative Embodiment No. 91 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 90, wherein the hydrophobic surface exhibits a moisturepenetration delay of at least about 5 seconds.

Alternative Embodiment No. 92 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 91, wherein the hydrophobic surface exhibits a moisturepenetration delay of at least about 10 seconds.

Alternative Embodiment No. 93 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 92, wherein the hydrophobic surface exhibits a moisturepenetration delay of at least about 20 seconds.

Alternative Embodiment No. 94 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, wherein moisture applied to the hydrophobic surfacedoes not migrate substantially in a lateral direction on the hydrophobicsurface of the sheet.

Alternative Embodiment No. 95 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 94, wherein moisture applied to the hydrophobic surfaceof the sheet migrates laterally in the sheet as it penetrates the sheet.

Alternative Embodiment No. 96 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 95, wherein moisture applied to the hydrophobic surfaceof the sheet migrates laterally progressively increasing distances withincreasing penetration into the sheet.

Alternative Embodiment No. 97 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, wherein the fused wax residue is localized at thehydrophobic surface of the sheet.

Alternative Embodiment No. 98 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, wherein the amount of fused wax residue in the sheetdecreases in a direction inwardly into the sheet from the laterallyhydrophobic surface.

Alternative Embodiment No. 99 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, wherein the amount of emulsifier residue increases ina direction inwardly into the sheet from the laterally hydrophobicsurface.

Alternative Embodiment No. 100 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, further comprising indicia identifying thehydrophobic surface of the sheet.

Alternative Embodiment No. 101 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, further comprising indicia identifying thehydrophilic surface of the sheet.

Alternative Embodiment No. 102 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, having a basis weight of from about 7 lbs per 3000square foot ream to about 35 lbs per 3000 square foot ream.

Alternative Embodiment No. 103 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, prepared from a creped cellulosic web.

Alternative Embodiment No. 104 is the sided absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 103, prepared from a creped cellulosic web having abiaxially undulatory structure.

Alternative Embodiment No. 105 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 82, wherein the web exhibits an air permeability of at least 25percent of the air permeability of a like web untreated with the aqueouswax dispersion.

Alternative Embodiment No. 106 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 105, wherein the web exhibits an air permeability of at least 40percent of the air permeability of a like web untreated with aqueous waxdispersion.

Alternative Embodiment No. 107 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 106, wherein the web exhibits an air permeability of at least 60percent of the air permeability of a like web untreated with the aqueouswax dispersion.

Alternative Embodiment No. 108 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 107, wherein the web exhibits an air permeability of at least 80percent of the air permeability of a like web untreated with the aqueouswax dispersion.

Alternative Embodiment No. 109 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 108, wherein the web exhibits substantially the same airpermeability as a like web of cellulosic fiber untreated with theaqueous wax dispersion.

Alternative Embodiment No. 110 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 82, wherein the web exhibits an air permeability of from about 15ft³/min-ft² to about 45 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 111 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 82, wherein the web exhibits an air permeability of from about 50ft³/min-ft² to about 150 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 112 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 82, wherein the web exhibits a wet tensile strength that is lessthan about 135 percent of the wet tensile strength of a like webuntreated with the aqueous wax dispersion.

Alternative Embodiment No. 113 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 112, wherein the web exhibits a wet tensile strength that is lessthan about 125 percent of the wet tensile strength of a like webuntreated with the aqueous wax dispersion.

Alternative Embodiment No. 114 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 113, wherein the web exhibits a wet tensile strength that is lessthan about 115 percent of the w et tensile strength of a like webuntreated with the aqueous wax dispersion.

Alternative Embodiment No. 115 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 114, wherein the web exhibits a wet tensile strength that is lessthan about 110 percent of the wet tensile strength of a like webuntreated with the aqueous wax dispersion.

Alternative Embodiment No. 116 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 115, wherein the web exhibits substantially the same wet tensilestrength as a like web of cellulosic fiber untreated with the aqueouswax dispersion position.

Alternative Embodiment No. 117 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 82, wherein the web exhibits substantially the same dry tensilestrength as a like web of cellulosic fiber untreated with the aqueouswax dispersion.

Alternative Embodiment No. 118 is the absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 82, wherein the web exhibits an absorbency of at least 60percent of that of a like web untreated with the aqueous wax dispersion.

Alternative Embodiment No. 119 is the absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 118, wherein the web exhibits an absorbency of at least75 percent of that of a like web untreated with the aqueous waxdispersion.

Alternative Embodiment No. 120 is the absorbent cellulosic webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 119, wherein the web exhibits an absorbency of at least90 percent of that of a like web untreated with the aqueous waxdispersion position.

Alternative Embodiment No. 121 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 120, wherein the web to moisture penetration exhibits substantiallythe same absorbency as a like web of cellulosic fiber untreated with theaqueous wax dispersion.

Alternative Embodiment No. 122 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 82, wherein the web exhibits an absorbency of at least 3 g/g.

Alternative Embodiment No. 123 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 122, wherein the web exhibits an absorbency of at least 6 g/g.

Alternative Embodiment No. 124 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 123, wherein the web exhibits an absorbency of at least 8 g/g.

Alternative Embodiment No. 125 is an absorbent wax-treated cellulosicweb comprising: an absorbent web of cellulosic fiber having ahydrophobic side and a hydrophilic side; wherein the hydrophobic sidecomprises at least one surfactant and at least one wax; wherein at leastone wax is substantially fused to the fibers; wherein the hydrophobicside allows water applied to the hydrophobic side to eventually diffuseinto the hydrophilic side; and wherein water applied to the hydrophobicside diffuses into the hydrophilic side and laterally diffuses in thehydrophilic side, prior to substantial lateral diffusion of the water onthe hydrophobic side.

Alternative Embodiment No. 126 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 125, wherein the web exhibits an air permeability of atleast 25 percent of the air permeability of a like web untreated withthe wax and emulsifier composition.

Alternative Embodiment No. 127 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 126, wherein the web exhibits an air permeability of atleast 40 percent of the air permeability of a like web untreated withthe wax and emulsifier composition.

Alternative Embodiment No. 128 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 127, wherein the web exhibits an air permeability of atleast 60 percent of the air permeability of a like web untreated withthe wax and emulsifier composition.

Alternative Embodiment No. 129 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 128, wherein the web exhibits an air permeability of atleast 80 percent of the air permeability of a like web untreated withthe wax and emulsifier composition.

Alternative Embodiment No. 130 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 129, wherein the web exhibits substantially the same airpermeability as a like web of cellulosic fiber untreated with the waxand emulsifier composition.

Alternative Embodiment No. 131 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 125, wherein the web exhibits an air permeability of fromabout 15 ft³/min-ft² to about 45 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 132 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 125, wherein the web exhibits an air permeability of fromabout 50 ft³/min-ft² to about 150 ft³/min-ft² at 0.5 inches of water.

Alternative Embodiment No. 133 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 125, wherein the web to moisture penetration exhibitssubstantially the same absorbency as a like web of cellulosic fiberuntreated with the wax and emulsifier composition.

Alternative Embodiment No. 134 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 125, wherein the web exhibits an absorbency of at least 3g/g.

Alternative Embodiment No. 135 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 34, wherein the web exhibits an absorbency of at least 6g/g.

Alternative Embodiment No. 136 is the absorbent wax-treated webexhibiting resistance to moisture penetration according to AlternativeEmbodiment No. 135, wherein the web exhibits an absorbency of at least 8g/g.

Alternative Embodiment No. 137 is a wax-treated absorbent cellulosicweb, comprising: at least one absorbent web of cellulosic fiber having ahydrophobic side and a hydrophilic side; wherein the hydrophobic sidecomprises at least one nonionic surfactant and at least onemicrocrystalline wax; wherein at least one wax has a melting point ofabout 85° C.; wherein at least one wax is substantially fused to thefibers; wherein the hydrophobic side allows water applied to thehydrophobic side to eventually diffuse into the hydrophilic side;wherein water applied to the hydrophilic side is delayed from diffusingto the hydrophobic side; wherein the delay is at least about twoseconds; and wherein water applied to the hydrophobic side diffuses intothe hydrophilic side and laterally diffuses in the hydrophilic side,prior to lateral diffusion of the water on the hydrophobic side.

Alternative Embodiment No. 138 is an absorbent cellulosic web exhibitingresistance to moisture penetration comprising an absorbent web ofcellulosic fibers provided with a wax composition in intimate contactwith the fibers in the web generally assimilating the morphology of thefiber surfaces, the wax composition having no independent macrostructureand being disposed in the web so that the open interstitialmicrostructure between fibers in the web is substantially preserved andwherein the web exhibits an absorbency of at least 3 g/g.

Alternative Embodiment No. 139 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 138, wherein the web exhibits an absorbency of at least 6 g/g.

Alternative Embodiment No. 140 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 138, wherein the web exhibits an absorbency of at least 8 g/g.

Alternative Embodiment No. 141 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 138, wherein the web exhibits an air permeability of at least 25percent of the air permeability of a like web untreated with the aqueouswax dispersion.

Alternative Embodiment No. 142 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 138, wherein the web exhibits an air permeability of at least 40percent of the air permeability of a like web untreated with aqueous waxdispersion.

Alternative Embodiment No. 143 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 138, wherein the web exhibits an air permeability of at least 60percent of the air permeability of a like web untreated with the aqueouswax dispersion.

Alternative Embodiment No. 144 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 138, wherein the web exhibits an air permeability of at least 80percent of the air permeability of a like web untreated with the aqueouswax dispersion.

Alternative Embodiment No. 145 is the absorbent web exhibitingresistance to moisture penetration according to Alternative EmbodimentNo. 138, wherein the web exhibits substantially the same airpermeability as a like web of cellulosic fiber untreated with theaqueous wax dispersion.

Alternative Embodiment No. 146 is a method of making an absorbentcellulosic web comprising: depositing a cellulosic papermaking furnishon a foraminous support; dewatering the papermaking furnish to produce aweb comprising cellulosic fibers; rendering at least one surface of theweb laterally hydrophobic by applying a fused wax dispersion thereto,the process of applying the fused wax dispersion including: wetting atleast one surface of the web with an aqueous dispersion including a waxand an emulsifier; and heating the web above the melting point of thewax to fuse the wax of the dispersion and to provide a hydrophobicsurface on the web, the surface being more hydrophobic than the web ofcellulosic fibers.

Alternative Embodiment No. 147 is the method according to AlternativeEmbodiment No. 146, wherein the heat tolerance limit of the web is notexceeded while fusing the wax.

Alternative Embodiment No. 148 is the method according to AlternativeEmbodiment No. 147, wherein the wax dispersion is applied to the web inan amount of from about 1 to about 20 weight percent on a dry basis.

Alternative Embodiment No. 149 is the method according to AlternativeEmbodiment No. 148, wherein the wax dispersion is applied to the web inan amount of from about 2 to about 10 weight percent on a dry basis.

Alternative Embodiment No. 150 is the method according to AlternativeEmbodiment No. 149, wherein the wax dispersion is applied to the web inan amount of from about 3 to about 5 weight percent on a dry basis.

Alternative Embodiment No. 151 is the method according to AlternativeEmbodiment No. 146, wherein the wax dispersion is wetted onto the web byway of spraying it onto the web.

Alternative Embodiment No. 152 is the method according to AlternativeEmbodiment No. 146, wherein the wax dispersion is wetted onto the web byway of printing it onto the web.

Alternative Embodiment No. 153 is the method according to AlternativeEmbodiment No. 152, wherein the wax dispersion is wetted onto the web byway of gravure printing.

Alternative Embodiment No. 154 is the method according to AlternativeEmbodiment No. 152, wherein the wax dispersion is wetted onto the web byway of printing it onto the web with a smooth printing roll.

Alternative Embodiment No. 155 is the method according to AlternativeEmbodiment No. 154, wherein the wax dispersion is wetted onto the web byway of offset printing with a smooth rubber application roll.

Alternative Embodiment No. 156 is the method according to AlternativeEmbodiment No. 146, wherein the step of heating the web above themelting temperature of the wax comprises heating the web with athroughdryer.

Alternative Embodiment No. 157 is the method according to AlternativeEmbodiment No. 146, wherein the step of heating the web above themelting temperature of the wax comprises heating the web with animpingement-air dryer.

Alternative Embodiment No. 158 is the method according to AlternativeEmbodiment No. 146, wherein the step of heating the web above themelting temperature of the wax comprises heating the web with a candryer.

Alternative Embodiment No. 159 is the method according to AlternativeEmbodiment No. 146, wherein the process of applying the fused waxdispersion includes wetting an aqueous wax dispersion onto both sides ofthe web.

Alternative Embodiment No. 160 is a method of making an absorbentcellulosic sheet comprising: depositing a cellulosic papermaking furnishon a foraminous support; dewatering the papermaking furnish to form aweb comprising cellulosic fibers; adhering the dewatered web to a Yankeedryer and drying the web to a consistency of greater than 50 percent;creping the web from the Yankee dryer; subsequent to the step of crepingthe web from the Yankee dryer, rendering at least one surface of the weblaterally hydrophobic by applying a fused wax dispersion thereto, theprocess of applying the fused wax dispersion including: wetting at leastone surface of the web with an aqueous dispersion including a wax and anemulsifier; and heating the web above the melting temperature of the waxto fuse the wax of the dispersion and to provide a hydrophobic surfaceon the web, the hydrophobic surface being more hydrophobic than the webof cellulosic fibers.

Alternative Embodiment No. 161 is the method according to AlternativeEmbodiment No. 160, wherein the heat tolerance limit of the web is notexceeded while fusing the wax.

Alternative Embodiment No. 162 is the method according to AlternativeEmbodiment No. 160, wherein the step of dewatering the web comprisesthroughdrying the web.

Alternative Embodiment No. 163 is the method according to AlternativeEmbodiment No. 160, wherein the web is creped from the Yankee dryer at aconsistency of at least about 95 percent.

Alternative Embodiment No. 164 is the method according to AlternativeEmbodiment No. 160, wherein the web is creped from the Yankee dryer at aconsistency of greater than about 50 percent and less than about 95percent.

Alternative Embodiment No. 165 is the method according to AlternativeEmbodiment No. 160, wherein the web is creped from the Yankee dryer at aconsistency of from about 60 to about 80 percent.

Alternative Embodiment No. 166 is the method according to AlternativeEmbodiment No. 160, wherein the web is creped from the Yankee dryerusing an undulatory creping blade.

Alternative Embodiment No. 167 is a method of making an absorbentcellulosic web resistant to moisture penetration comprising: wetting atleast one surface of the web with an aqueous dispersion including a waxand an emulsifier; and heating the wetted web above the meltingtemperature of the wax to fuse the wax of the dispersion and to providea hydrophobic surface on the web, the hydrophobic surface being morehydrophobic than the corresponding surface of the untreated web, whereinthe wax-treated web exhibits an air permeability of at least about 25percent of the air permeability of the untreated web.

Alternative Embodiment No. 168 is the method according to AlternativeEmbodiment No. 167, wherein the wax-treated web exhibits an airpermeability of at least about 40 percent of the air permeability of thetreated web.

Alternative Embodiment No. 169 is the method according to AlternativeEmbodiment No. 168, wherein the wax-treated web exhibits an airpermeability of at least about 60 percent of the air permeability of thetreated web.

Alternative Embodiment No. 170 is the method according to AlternativeEmbodiment No. 169, wherein the wax-treated web exhibits an airpermeability of at least about 80 percent of the air permeability of thetreated web.

Alternative Embodiment No. 171 is the method according to AlternativeEmbodiment No. 170, wherein the wax-treated web exhibits an airpermeability substantially the same as the untreated web.

Alternative Embodiment No. 172 is the method according to AlternativeEmbodiment No. 167, wherein the wax-treated web exhibits an airpermeability of from about 15 ft³/min-ft² to about 45 ft³/min-ft² at 0.5inches of water.

Alternative Embodiment No. 173 is the method according to AlternativeEmbodiment No. 172, wherein the wax-treated web exhibits an airpermeability of from about 50 ft³/min-ft² to about 150 ft³/min-ft² at0.5 inches of water.

Alternative Embodiment No. 174 is the method according to AlternativeEmbodiment No. 167, wherein the wax dispersion is wetted onto the web byway of spraying it onto the web.

Alternative Embodiment No. 175 is the method according to AlternativeEmbodiment No. 167, wherein the wax dispersion is wetted onto the web byway of printing it onto the web.

Alternative Embodiment No. 176 is the method according to AlternativeEmbodiment No. 175, wherein the wax dispersion is wetted onto the web byway of gravure printing.

Alternative Embodiment No. 177 is the method according to AlternativeEmbodiment No. 175, wherein the wax dispersion is wetted onto the web byway of printing it onto the web with a smooth printing roll.

Alternative Embodiment No. 178 is the method according to AlternativeEmbodiment No. 177, wherein the wax dispersion is wetted onto the web byway of offset printing with a smooth rubber application roll.

Alternative Embodiment No. 179 is the method according to AlternativeEmbodiment No. 175, wherein the wax dispersion is printed onto bothsides of the absorbent cellulosic sheet.

Alternative Embodiment No. 180 is the method according to AlternativeEmbodiment No. 167, further comprising the step of heating the aqueouswax dispersion immediately prior to applying it to the sheet.

Alternative Embodiment No. 181 is the method according to AlternativeEmbodiment No. 180, wherein the step of heating the aqueous dispersionis operative to increase the solids content of the aqueous dispersion.

Alternative Embodiment No. 182 is the method according to AlternativeEmbodiment No. 180, wherein the step of heating the aqueous waxdispersion is operative to at least partially melt the wax.

Alternative Embodiment No. 183 is the method according to AlternativeEmbodiment No. 167, wherein the aqueous wax dispersion is wetted ontothe web with an applicator roll and wherein the aqueous wax dispersionis heated while in contact with the applicator roll.

Alternative Embodiment No. 184 is the method according to AlternativeEmbodiment No. 183, wherein the step of heating the aqueous waxdispersion is operative to increase the solids content of the aqueouswax dispersion.

Alternative Embodiment No. 185 is the method according to AlternativeEmbodiment No. 183, wherein the step of heating the aqueous waxdispersion is operative to at least partially melt the wax.

Alternative Embodiment No. 186 is a method of making an absorbentcellulosic web resistant to moisture penetration comprising: wetting atleast one surface of the web with an aqueous dispersion including a waxand an emulsifier; and heating the wetted web above the meltingtemperature of the wax to fuse the wax of the dispersion and to providea hydrophobic surface on the web, the hydrophobic surface being morehydrophobic than the corresponding surface of the untreated web, whereinthe wax-treated web exhibits a wet tensile strength that is less than about 135 percent of wet tensile strength of the untreated web.

Alternative Embodiment No. 187 is the method according to AlternativeEmbodiment No. 186, wherein the wax-treated web exhibits a wet tensilestrength which is less than about 125 percent of wet tensile strength ofthe untreated web.

Alternative Embodiment No. 188 is the method according to AlternativeEmbodiment No. 187, wherein the wax-treated web exhibits a wet tensilestrength which is less than about 115 percent of wet tensile strength ofthe untreated web.

Alternative Embodiment No. 189 is the method according to AlternativeEmbodiment No. 188, wherein the wax-treated web exhibits a wet tensilestrength which is less than about 110 percent of wet tensile strength ofthe untreated web.

Alternative Embodiment No. 190 is the method according to AlternativeEmbodiment No. 189, wherein the wax-treated web exhibits a wet tensilestrength substantially the same as the untreated web.

Alternative Embodiment No. 191 is a method of making an absorbentcellulosic web resistant to moisture penetration comprising: wetting atleast one surface of the web with an aqueous dispersion including a waxand an emulsifier; and heating the wetted web above the meltingtemperature of the wax to fuse the wax of the dispersion and to providea hydrophobic surface on the web, wherein the hydrophobic surface of thewax-treated web exhibits a contact angle with water which is at leastabout 20 degrees greater at one minute than the contact angle of thecorresponding surface of the web prior to treatment at one minute.

Alternative Embodiment No. 192 is the method of making an absorbentcellulosic web resistant to moisture penetration according toAlternative Embodiment No. 191, wherein the contact angle with water ofthe hydrophobic surface of the treated web at one minute is at leastabout 40 degrees greater than the contact angle of the correspondingsurface of the web prior to treatment at one minute.

Alternative Embodiment No. 193 is the method of making an absorbentcellulosic web resistant to moisture penetration according toAlternative Embodiment No. 192, wherein the contact angle with water ofthe hydrophobic surface of the treated web at one minute is at leastabout 60 degrees greater than the contact angle of the correspondingsurface of the web prior to treatment at one minute.

Alternative Embodiment No. 194 is the method of making an absorbentcellulosic web resistant to moisture penetration according toAlternative Embodiment No. 193, wherein the contact angle with water ofthe hydrophobic surface of the treated web at one minute is at leastabout 80 degrees greater than the contact angle of the correspondingsurface of the web prior to treatment at one minute.

Alternative Embodiment No. 195 is a method of controlling microbialcontamination comprising: providing an absorbent barrier sheet formedfrom a web of cellulosic fibers provided with a fused wax composition inintimate contact with the fibers in the web generally assimilating themorphology of the fiber surfaces, the fused wax composition including awax and an emulsifier and being disposed in the web so that the openinterstitial microstructure between fibers in the web is substantiallypreserved; interposing the absorbent barrier sheet between a microbialcontamination source and its surroundings, the absorbent sheet beingeffective to impede migration of the microbial contamination sourcetherethrough.

Alternative Embodiment No. 196 is the method according to AlternativeEmbodiment No. 195, wherein said microbial contamination sourcecomprises a bacterial contamination source.

Alternative Embodiment No. 197 is the method according to AlternativeEmbodiment No. 196, wherein the bacterial contamination source comprisesa staphylococcus bacteria.

Alternative Embodiment No. 198 is the method according to AlternativeEmbodiment No. 196, wherein the bacterial contamination source comprisesan E. coli bacteria.

Alternative Embodiment No. 199 is the method according to AlternativeEmbodiment No. 196, wherein the bacterial contamination source comprisesa streptococcus bacteria.

Alternative Embodiment No. 200 is the method according to AlternativeEmbodiment No. 196, wherein the bacterial contamination source comprisesa salmonella bacteria.

Alternative Embodiment No. 201 is the method according to AlternativeEmbodiment No. 195, wherein the microbial composition comprises an alga.

Alternative Embodiment No. 202 is the method according to AlternativeEmbodiment No. 195, wherein the microbial contamination source comprisesa fungus.

Alternative Embodiment No. 203 is the method according to AlternativeEmbodiment No. 195, wherein the microbial contamination source comprisesa virus.

Alternative Embodiment No. 204 is the method according to AlternativeEmbodiment No. 203, wherein the virus is a rhino virus.

Alternative Embodiment No. 205 is the method according to AlternativeEmbodiment No. 203, wherein the virus is an influenza virus.

Alternative Embodiment No. 206 is a method of controlling microbialcontamination comprising: providing an absorbent barrier sheet formedfrom a web of cellulosic fibers provided with a fused wax composition inintimate contact with the fibers in the web generally assimilating themorphology of the fiber surfaces, the fused wax composition including awax and an emulsifier and being disposed in the web so that the openinterstitial microstructure between fibers in the web is substantiallypreserved; covering a substrate with the absorbent barrier sheet, theabsorbent sheet being effective to impede migration from a microbialcontamination source to the substrate.

Alternative Embodiment No. 207 is the method according to AlternativeEmbodiment No. 206, wherein said microbial contamination sourcecomprises a bacterial contamination source.

Alternative Embodiment No. 208 is the method according to AlternativeEmbodiment No. 207, wherein the bacterial contamination source comprisesa staphylococcus bacteria.

Alternative Embodiment No. 209 is the method according to AlternativeEmbodiment No. 207, wherein the bacterial contamination source comprisesan E. coli bacteria.

Alternative Embodiment No. 210 is the method according to AlternativeEmbodiment No. 207, wherein the bacterial contamination source comprisesa streptococcus bacteria.

Alternative Embodiment No. 211 is the method according to AlternativeEmbodiment No. 207, wherein the bacterial contamination source comprisesa salmonella bacteria.

Alternative Embodiment No. 212 is the method according to AlternativeEmbodiment No. 206, wherein the microbial composition comprises an alga.

Alternative Embodiment No. 213 is the method according to AlternativeEmbodiment No. 206, wherein the microbial contamination source comprisesa fungus.

Alternative Embodiment No. 214 is the method according to AlternativeEmbodiment No. 206, wherein the microbial contamination source comprisesa virus.

Alternative Embodiment No. 215 is the method according to AlternativeEmbodiment No. 214, wherein the virus is a rhino virus.

Alternative Embodiment No. 216 is the method according to AlternativeEmbodiment No. 214, wherein the virus is an influenza virus.

Alternative Embodiment No. 217 is the method according to AlternativeEmbodiment No. 214, wherein the virus is a corona virus of the classbelieved to cause severe acute respiratory syndrome (SARS) in humans.

Alternative Embodiment No. 218 is a multi-ply absorbent structurecomprising a plurality of wax-treated plies exhibiting resistance tomoisture penetration having at least two contiguous wax-treated plieseach of which comprises an absorbent web of cellulosic fibers providedwith a fused composition in intimate contact with the fibers in the webgenerally assimilating the morphology of the fiber surfaces, the fusedcomposition including a wax and an emulsifier and being disposed in theweb so that the open interstitial microstructure between fibers in theweb is substantially preserved and wherein further the multi-plyabsorbent structure is characterized by a resistance to moisturepenetration greater than its constituent plies.

Alternative Embodiment No. 219 is the multilayer absorbent structureaccording to Alternative Embodiment No. 218, wherein the multilayerabsorbent structure is a folded napkin including at least one plyconsisting of the wax treated absorbent sheet.

Alternative Embodiment No. 220 is the multilayer absorbent structureaccording to Alternative Embodiment No. 219, wherein the multilayerabsorbent structure is a folded napkin including at least two pliesconsisting of the wax treated absorbent sheet.

Alternative Embodiment No. 221 is the multilayer absorbent structureaccording to Alternative Embodiment No. 218, wherein the multilayerabsorbent structure is a two-ply folded napkin wherein one ply consistsof the wax treated absorbent sheet and the other ply consists of anabsorbent sheet of cellulosic fiber which is untreated with wax.

Alternative Embodiment No. 222 is the multilayer absorbent structureaccording to Alternative Embodiment No. 218, wherein the multilayerabsorbent structure is in the form of a two panel folded napkin.

Alternative Embodiment No. 223 is the multilayer absorbent structureaccording to Alternative Embodiment No. 218, wherein the multilayerabsorbent structure is in the form of a four panel folded napkin.

Alternative Embodiment No. 224 is a multi-ply absorbent sheet comprisinga plurality of absorbent cellulosic plies bonded together wherein atleast a first treated ply is a wax treated cellulosic ply exhibitingresistance to moisture penetration wherein the wax treated cellulosicply comprises an absorbent web of cellulosic fiber and the fused residueof an aqueous wax dispersion applied to one side thereof, wherein thefirst treated ply has a laterally hydrophobic surface and a relativelyhydrophilic surface such that the contact angle of the laterallyhydrophobic surface with water is at least about 5 degrees greater thanthe contact angle of the relatively hydrophilic surface with water andwherein the hydrophobic surface exhibits a moisture penetration delay offrom about 3 to about 40 seconds.

Alternative Embodiment No. 225 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 224, wherein the hydrophobicsurface of the first wax-treated ply has a contact angle with water atleast about 10 degrees greater than the contact angle with water of therelatively hydrophilic surface.

Alternative Embodiment No. 226 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 225, wherein the hydrophobicsurface of the first wax-treated ply has a contact angle with water atleast about 15 degrees greater than the contact angle with water of therelatively hydrophilic surface.

Alternative Embodiment No. 227 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 226, wherein the hydrophobicsurface of the first wax-treated ply has a contact angle with water atleast about 20 degrees greater than the contact angle with water of therelatively hydrophilic surface.

Alternative Embodiment No. 228 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 227, wherein the hydrophobicsurface of the first wax-treated ply has a contact angle with water atleast about 40 degrees greater than the contact angle with water of therelatively hydrophilic surface.

Alternative Embodiment No. 229 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 228, wherein the hydrophobicsurface of the first wax-treated ply has a contact angle with water atleast about 80 degrees greater than the contact angle with water of therelatively hydrophilic surface.

Alternative Embodiment No. 230 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 224, wherein the hydrophobicsurface of the first treated ply is internally disposed in the product.

Alternative Embodiment No. 231 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 224, wherein at least two pliesare glue-bonded.

Alternative Embodiment No. 232 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 224, further comprising a secondtreated ply comprising a wax treated cellulosic ply exhibitingresistance to moisture penetration wherein the wax treated cellulosicply comprises an absorbent web of cellulosic fiber and the fused residueof an aqueous wax dispersion applied to one side thereof, wherein thesecond treated ply has a laterally hydrophobic surface and a relativelyhydrophilic surface such that the contact angle of the laterallyhydrophobic surface with water is at least about 5 degrees greater thanthe contact angle of the relatively hydrophilic surface with water andwherein the hydrophobic surface of the second treated ply exhibits amoisture penetration delay of from about 3 to about 40 seconds.

Alternative Embodiment No. 233 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 232, wherein the hydrophobicsurfaces of the first and second treated plies are internally disposedin the multi-ply sheet.

Alternative Embodiment No. 234 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 233, wherein the hydrophobicsurfaces of said first and second treated plies are in contact with oneanother.

Alternative Embodiment No. 235 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 234, in the form of a napkin.

Alternative Embodiment No. 236 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 232, wherein the hydrophobicsurface of the first absorbent ply is internally disposed in the sheetand the hydrophobic surface of the second treated ply is an outersurface of the product.

Alternative Embodiment No. 237 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 232, wherein the hydrophobicsurface of the first treated ply is an outer surface of the sheet andthe hydrophobic surface of the second treated ply is the other outersurface of the sheet.

Alternative Embodiment No. 238 is a multi-ply absorbent sheet comprisinga plurality of absorbent cellulosic plies bonded together including awax-treated ply, wherein the wax-treated ply comprises an absorbent webof cellulosic fibers provided with a fused composition in intimatecontact with the fibers in the web generally assimilating the morphologyof the fiber surfaces, the fused composition including a wax and anemulsifier and being disposed in the web so that the open interstitialmicrostructure between fibers in the ply is substantially preserved.

Alternative Embodiment No. 239 is the multi-ply absorbent sheetaccording to Alternative Embodiment No. 238, wherein the wax treated plyis internally disposed in the sheet between two outer plies.

Alternative Embodiment No. 240 is the multi-ply sheet according toAlternative Embodiment No. 238, wherein the sheet is a 3 ply sheet witha central wax treated ply.

Alternative Embodiment No. 241 is the multi-ply sheet according toAlternative Embodiment No. 240, in the form of a three-ply napkin.

Alternative Embodiment No. 242 is a method of making a multiplyabsorbent sheet which resists moisture penetration comprising: preparinga moisture penetration resistant treated cellulosic ply by way of:providing an absorbent cellulosic web; wetting one surface of the webwith an aqueous dispersion including a wax and an emulsifier; andheating the web above the melting temperature of the wax to fuse the waxof the dispersion and to provide a hydrophobic surface on the web, thehydrophobic surface being more hydrophobic than the web of cellulosicfiber; applying an adhesive to the treated ply; and bonding the treatedply to a second cellulosic ply.

Alternative Embodiment No. 243 is the method according to AlternativeEmbodiment No. 232, wherein the adhesive is applied to a surface of thetreated ply that was wetted with the aqueous dispersion.

Alternative Embodiment No. 244 is the method according to AlternativeEmbodiment No. 232, wherein the second ply is an untreated ply.

Alternative Embodiment No. 245 is the method according to AlternativeEmbodiment No. 232, wherein the plies are bonded to each other in apress nip.

Alternative Embodiment No. 246 is the method according to AlternativeEmbodiment No. 242, wherein the adhesive is printed onto the treatedply.

Alternative Embodiment No. 247 is an absorbent composite comprising anabsorbent core and a cover sheet disposed thereon, the cover sheetconsisting of an absorbent cellulosic sheet exhibiting resistance tomoisture penetration including an absorbent web of cellulosic fibersprovided with a fused composition in intimate contact with the fibers inthe web generally assimilating the morphology of the fiber surfaces, thefused composition including a wax and an emulsifier and being disposedin the web so that the open interstitial microstructure between fibersin the ply is substantially preserved.

Alternative Embodiment No. 248 is the absorbent composite according toAlternative Embodiment No. 247, wherein the absorbent core comprisescellulosic fiber.

Alternative Embodiment No. 249 is the absorbent composite according toAlternative Embodiment No. 242, wherein the absorbent core comprisessuperabsorbent polymer.

Alternative Embodiment No. 250 is the absorbent composite according toAlternative Embodiment No. 249, wherein the superabsorbent polymer is anacrylic acid polymer.

Alternative Embodiment No. 251 is the absorbent composite according toAlternative Embodiment No. 247, wherein the outer surface of the coverlayer is laterally hydrophobic with respect to its inner portion suchthat moisture applied to the outer surface of the cover layer migratesinwardly and laterally in the cove r layer beneath the outer surface toa greater extent than it migrates laterally at the outer surface.

Alternative Embodiment No. 252 is the absorbent composite according toAlternative Embodiment No. 251, wherein moisture applied to the outersurface of the cover layer does not migrate substantially on the outersurface in a lateral direction.

Alternative Embodiment Nos. 253-260 are directed to respirators such assurgical masks (N95 respirators) and the like (e.g., N100 respirators)for limiting airborne microbial contamination. Specifically, filtermedia for such devices and the devices themselves are contemplatedwithin the scope of the present invention.

Alternative Embodiment No. 253 is a filter media for a respiratorcomprising an absorbent web of cellulosic fibers provided with a waxcomposition in intimate contact with the fibers in the web generallyassimilating the morphology of the fiber surfaces, the wax compositionhaving no independent macrostructure and being disposed in the web sothat the open interstitial microstructure between fibers in the web issubstantially preserved and wherein the web exhibits an absorbency of atleast 3 g/g.

Alternative Embodiment No. 254 is the filter media according toAlternative Embodiment No. 253, wherein the web exhibits an absorbencyof at least 6 g/g.

Alternative Embodiment No. 255 is the filter media according toAlternative Embodiment No. 253, wherein the web exhibits an absorbencyof at least 8 g/g.

Alternative Embodiment No. 256 is the filter media according toAlternative Embodiment No. 253, wherein the web exhibits an airpermeability of at least 25 percent of the air permeability of a likeweb untreated with the aqueous wax dispersion.

Alternative Embodiment No. 257 is the filter media according toAlternative Embodiment No. 253, wherein the web exhibits an airpermeability of at least 40 percent of the air permeability of a likeweb untreated with aqueous wax dispersion.

Alternative Embodiment No. 258 is the filter media according toAlternative Embodiment No. 253, wherein the web exhibits an airpermeability of at least 60 percent of the air permeability of a likeweb untreated with the aqueous wax dispersion.

Alternative Embodiment No. 259 is the filter media according toAlternative Embodiment No. 253 wherein the web exhibits an airpermeability of at least 80 percent of the air permeability of a likeweb untreated with the aqueous wax dispersion.

Alternative Embodiment No. 260 is the filter media according toAlternative Embodiment No. 253, wherein the web exhibits substantiallythe same air permeability as a like web of cellulosic fiber untreatedwith the aqueous wax dispersion.

Alternative Embodiment No. 261 is a tissue having a basis weight of fromabout 15 to about 30 lbs per 3000 square foot ream exhibiting resistanceto wet-through from propelled liquid incident thereon, comprising acellulosic web treated with the heat fused residue of a wax emulsionapplied thereto, the tissue exhibiting liquid penetration barrierproperties such that less than about 20 percent of liquid sorbed from0.1 ml thereof propelled to one surface of the tissue in a sneezesimulation test will penetrate to the surface of the tissue opposite tothe insult.

Alternative Embodiment No. 262 is a tissue having a basis weight of fromabout 15 to about 30 lbs per 3000 square foot ream exhibiting resistanceto wet-through from propelled liquid incident thereon, comprising acellulosic web treated with the heat fused residue of a wax emulsionapplied thereto, the tissue exhibiting liquid penetration barrierproperties such that less than about 10 percent of liquid sorbed from0.1 ml thereof propelled to one surface of the tissue in a sneezesimulation test will penetrate to the surface of the tissue opposite tothe insult.

Alternative Embodiment No. 263 is a tissue having a basis weight of fromabout 15 to about 30 lbs per 3000 square foot ream exhibiting resistanceto wet-through from propelled liquid incident thereon, comprising acellulosic web treated with the heat fused residue of a wax emulsionapplied thereto, the tissue exhibiting liquid penetration barrierproperties such that less than about 5 percent of liquid sorbed from a0.1 ml insult propelled to one surface of the tissue in a sneezesimulation test will penetrate to the surface of the tissue opposite tothe insult.

Alternative Embodiment No. 264 is the tissue according to AlternativeEmbodiment No. 261, wherein the tissue is a 1 ply tissue.

Alternative Embodiment No. 265 is the tissue according to AlternativeEmbodiment No. 261, wherein the tissue is a 2 ply tissue.

Alternative Embodiment No. 266 is the tissue according to AlternativeEmbodiment No. 261, wherein the tissue is a 3 ply tissue.

Alternative Embodiment No. 267 is a tissue having a basis weight of fromabout 15 to about 30 lbs per 3000 square foot ream exhibiting resistanceto wet-through from propelled liquid incident thereon, comprising acellulosic web treated with the heat fused residue of a wax emulsionapplied thereto, wherein the liquid sorbed from liquid propelled to onesurface of the tissue will exhibit a maximum concentration at thecentral portion of the tissue, wherein that maximum concentration is atleast about 1.25 times the concentration of the liquid sorbed at thesurface portion proximate the vicinity of impact and wherein the maximumis at least about 2.5 times the concentration of liquid sorbed from theinsult at the surface portion distal to impact.

Alternative Embodiment No. 268 is a method of measuring the resistanceof tissue to liquid penetration by a simulated sneeze comprising thesteps of positioning a target sample of tissue and propelling apredetermined amount of liquid to the target sample followed bymeasuring the penetration of the liquid into the sample.

Alternative Embodiment No. 269 is the embodiment according toAlternative Embodiment No. 268, wherein the predetermined amount ofliquid is from about 0.25 to about 4 ml of liquid.

Alternative Embodiment No. 270 is the embodiment according toAlternative Embodiment No. 268, wherein the predetermined amount ofliquid is from about 0.5 to about 1.5 ml of liquid.

Alternative Embodiment No. 271 is the embodiment according toAlternative Embodiment No. 268, wherein the liquid is propelled by apneumatic pressure source having a pressure of from about 5 psig toabout 75 psig.

Alternative Embodiment No. 272 is the embodiment according toAlternative Embodiment No. 268, wherein the liquid is propelled by apneumatic pressure source having a pressure of from about 10 psig toabout 50 psig.

Alternative Embodiment No. 273 is the embodiment according toAlternative Embodiment No. 268, wherein the liquid is propelled by apneumatic pressure source having a pressure of from about 15 psig toabout 30 psig.

Alternative Embodiment No. 274 is the embodiment according toAlternative Embodiment No. 268, wherein the target sample is positionedin a chamber under substantially ambient conditions.

Alternative Embodiment No. 275 is the embodiment according toAlternative Embodiment No. 268, wherein the penetration of liquid ischaracterized as a function of distance from the impact of the testliquid.

Alternative Embodiment No. 276 is the embodiment according toAlternative Embodiment No. 268, wherein the target sample of tissue is amulti-ply sample of tissue.

Alternative Embodiment No. 277 is the embodiment according toAlternative Embodiment No. 268, wherein the target sample of tissue hasfrom 2 to 8 separable plies.

Alternative Embodiment No. 278 is the embodiment according toAlternative Embodiment No. 268, wherein the target sample of tissue hasfrom 3 to 6 separable plies.

Alternative Embodiment No. 279 is the embodiment according toAlternative Embodiment No. 268, wherein the target sample of tissue is amulti-ply sample of separable plies, each of which plies has a basisweight of from about 7 to about 15 lbs. per 3000 square foot ream.

Alternative Embodiment No. 280 is the embodiment according toAlternative Embodiment No. 268, wherein the target sample of tissue is amulti-ply sample of separable plies, each of which plies has a basisweight of from about 9 to about 13 lbs. per 3000 square foot ream.

In a still further aspect of the present invention there is provided amethod and apparatus for testing tissue resistance to penetration bypropelled liquid to penetration by propelled liquid, that is, simulatinga sneeze and characterizing the resistance to moisture penetration.

1. An absorbent cellulosic web exhibiting resistance to moisturepenetration comprising an absorbent web of cellulosic fibers providedwith a fused wax composition in intimate contact with the fibers in theweb, the fused wax composition including a wax and an emulsifier fusedin situ with the web and being disposed in the web so that the openinterstitial microstructure between fibers in the web is substantiallypreserved and the web has a laterally hydrophobic surface.
 2. Theabsorbent web exhibiting resistance to moisture penetration according toclaim 1, wherein wax is present in an amount of from about 1 to about 20weight percent based on the amount of wax and cellulosic fiber in theweb.
 3. The absorbent sheet exhibiting resistance to moisturepenetration according to claim 2, wherein wax is present in an amount offrom about 2 to about 10 weight percent based on the amount of wax andcellulosic fiber in the web.
 4. The absorbent web exhibiting resistanceto moisture penetration according to claim 2, wherein wax is present inan amount of from about 3 to about 5 weight percent based on the amountof wax and cellulosic fiber in the web.
 5. The absorbent web exhibitingresistance to moisture penetration according to claim 2, wherein the webexhibits an absorbency of at least 3 g/g.
 6. The absorbent webexhibiting resistance to moisture penetration according to claim 5,wherein the web exhibits an absorbency of at least 6 g/g.
 7. Anabsorbent cellulosic web exhibiting resistance to moisture penetrationcomprising an absorbent web of cellulosic fibers provided with a fusedwax composition in intimate contact with the fibers in the web generallyassimilating the morphology of the fiber surfaces, the fused waxcomposition including a wax and an emulsifier and being disposed in theweb so that the open interstitial microstructure between fibers in theweb is substantially preserved and wherein the web exhibits anabsorbency of at least 3 g/g.
 8. The absorbent web exhibiting resistanceto moisture penetration according to claim 7, wherein the web exhibitsan absorbency of at least 6 g/g.
 9. The absorbent web exhibitingresistance to moisture penetration according to claim 8, wherein the webexhibits an absorbency of at least 8 g/g.
 10. The absorbent webexhibiting resistance to moisture penetration according to claim 7,wherein the web exhibits an air permeability of from about 15ft³/min-ft² to about 45 ft³/min-ft² at 0.5 inches of water.
 11. Theabsorbent web exhibiting resistance to moisture penetration according toclaim 7, wherein the web exhibits an air permeability of from about 50ft³/min-ft² to about 150 ft³/min-ft² at 0.5 inches of water.
 12. Anabsorbent cellulosic web exhibiting resistance to moisture penetrationcomprising an absorbent web of cellulosic fibers provided with a waxcomposition in intimate contact with the fibers in the web generallyassimilating the morphology of the fiber surfaces, the wax compositionhaving no independent macrostructure and being disposed in the web sothat the open interstitial microstructure between fibers in the web issubstantially preserved and wherein the web exhibits an absorbency of atleast 3 g/g.
 13. The absorbent web exhibiting resistance to moisturepenetration according to claim 12, wherein the web exhibits anabsorbency of at least 6 g/g.
 14. The absorbent web exhibitingresistance to moisture penetration according to claim 12, wherein theweb exhibits an absorbency of at least 8 g/g.
 15. The absorbent webexhibiting resistance to moisture penetration according to claim 12,wherein the web exhibits an air permeability of at least 25 percent ofthe air permeability of a like web untreated with the aqueous waxdispersion.
 16. The absorbent web exhibiting resistance to moisturepenetration according to claim 12, wherein the web exhibits an airpermeability of at least 40 percent of the air permeability of a likeweb untreated with aqueous wax dispersion.
 17. The absorbent webexhibiting resistance to moisture penetration according to claim 12,wherein the web exhibits an air permeability of at least 60 percent ofthe air permeability of a like web untreated with the aqueous waxdispersion.
 18. The absorbent web exhibiting resistance to moisturepenetration according to claim 12, wherein the web exhibits an airpermeability of at least 80 percent of the air permeability of a likeweb untreated with the aqueous wax dispersion.
 19. The absorbent webexhibiting resistance to moisture penetration according to claim 12,wherein the web exhibits substantially the same air permeability as alike web of cellulosic fiber untreated with the aqueous wax dispersion.20. The absorbent web exhibiting resistance to moisture penetrationaccording to claim 12, wherein wax is present in an amount of from about1 to about 20 weight percent based on the amount of wax and cellulosicfiber in the web.